US20190344310A1 - Method for forming multilayer coated film - Google Patents

Method for forming multilayer coated film Download PDF

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Publication number
US20190344310A1
US20190344310A1 US16/394,503 US201916394503A US2019344310A1 US 20190344310 A1 US20190344310 A1 US 20190344310A1 US 201916394503 A US201916394503 A US 201916394503A US 2019344310 A1 US2019344310 A1 US 2019344310A1
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United States
Prior art keywords
coated film
coating composition
resin
hydroxyl group
group
Prior art date
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Granted
Application number
US16/394,503
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US11541420B2 (en
Inventor
Kazuki Matsubara
Yoshinari Matsuura
Takayuki Ono
Hironori Tonomura
Masako Hase
Hiroshi Mitsuishi
Keiji AMBO
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Kansai Paint Co Ltd
Toyota Motor Corp
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Kansai Paint Co Ltd
Toyota Motor Corp
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Assigned to KANSAI PAINT CO., LTD., TOYOTA JIDOSHA KABUSHIKI KAISHA reassignment KANSAI PAINT CO., LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: MATSUBARA, KAZUKI, MATSUURA, YOSHINARI, ONO, TAKAYUKI, TONOMURA, HIRONORI, AMBO, KEIJI, HASE, Masako, MITSUISHI, HIROSHI
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
    • C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50—Multilayers
    • B05D7/56—Three layers or more
    • B05D7/57—Three layers or more the last layer being a clear coat
    • B05D7/572—Three layers or more the last layer being a clear coat all layers being cured or baked together
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/46—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen
    • C08G18/4615—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/50—Polyethers having heteroatoms other than oxygen
    • C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/54—Polycondensates of aldehydes
    • C08G18/544—Polycondensates of aldehydes with nitrogen compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
    • C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
    • C08G18/6225—Polymers of esters of acrylic or methacrylic acid
    • C08G18/6229—Polymers of hydroxy groups containing esters of acrylic or methacrylic acid with aliphatic polyalcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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    • C08G18/6415—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63 having nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
    • C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
    • C08G18/8064—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with monohydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
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    • C08G18/8093—Compounds containing active methylene groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/06—Polyurethanes from polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2202/00—Metallic substrate
    • B05D2202/10—Metallic substrate based on Fe
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
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    • B05D2202/00—Metallic substrate
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    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2350/00—Pretreatment of the substrate
    • B05D2350/60—Adding a layer before coating
    • B05D2350/65—Adding a layer before coating metal layer
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    • B05D2508/00—Polyesters

Definitions

  • the present invention relates to a method for forming a multilayer coated film for coating an automotive body, the multilayer coated film being excellent in the chipping resistance, the scratching resistance, the coated film hardness and the adhesive strength when bonding to a member.
  • a multilayer coated film including an undercoat film excellent in the anticorrosive property, an intermediate coated film excellent in the smoothness and chipping resistance (chipping: damage to a coated film caused when hit by a small pebble, etc. flying from road), and a top coated film excellent in the appearance and the scratching resistance and the coated film hardness, as resistance to an environmental load, is usually formed on a steel plate for the purpose of imparting excellent anticorrosive property and appearance.
  • the method of forming the multilayer coated film on the automobile body or the like as an object to be coated from a viewpoint of shortening a coating time and reducing CO 2 and VOC, the method of forming the multilayer coated film by the following aqueous 3 Wet system is used: after an aqueous intermediate coating composition is applied to perform intermediate coating, an aqueous color base coating composition is applied thereto to perform color base coating in a wet state as it is, and then, clear coating composition is also applied thereto to perform clear coating in the wet state, followed by burning them.
  • Patent Document 1 discloses a method for forming a coated film using an intermediate coating composition containing (a) a urethane-modified polyester resin obtained by reacting an aliphatic diisocyanate compound with a hydroxyl group-containing polyester resin obtained by polycondensation of an acid component containing 80 mol % or more of isophthalic acid, and a polyhydric alcohol; (b) a melamine resin; (c) a hexamethylene diisocyanate compound blocked by an active methylene group-containing compound; (d) a nonaqueous dispersion resin having a core-shell structure; and (e) a flat pigment.
  • a urethane-modified polyester resin obtained by reacting an aliphatic diisocyanate compound with a hydroxyl group-containing polyester resin obtained by polycondensation of an acid component containing 80 mol % or more of isophthalic acid, and a polyhydric alcohol
  • a melamine resin a hexamethylene di
  • Patent Document 2 discloses a multilayer coated film on an external panel of an automotive body, etc., which is a multilayer coated film having formed therein, in the following order, an electrodeposition coated film, an intermediate coated film, a base coated film and a clear coated film, wherein at ⁇ 20° C., the intermediate coated film has a Young's modulus of 35,000 kg/cm 2 or more and an elongation at break of 2% or less and the clear coated film has a Young's modulus of 35,000 kg/cm 2 or less and an elongation at break of 5% or more.
  • the scratching resistance is mainly achieved by imparting functions to the clear coat coating composition which forms the uppermost layer.
  • the clear coating composition containing a hydroxyl group-containing acrylic resin and a polyisocyanate compound is used for the purpose of improving the scratching resistance.
  • Patent Document 3 discloses a coating composition containing a hydroxyl group-containing resin (A) having a hydroxyl value of from 80 to 200 mgKOH/g and a weight average molecular weight of 2,500 to 40,000, a polyisocyanate compound (B), and a polycarbonate diol compound (C), as a diol component, having a viscosity at 50° C. of 10,000 mPa ⁇ s or less and a number average molecular weight of 400 to 2,500, obtained by reacting a diol having 2 to 10 carbon atoms with a carbonyl agent.
  • A hydroxyl group-containing resin
  • B polyisocyanate compound
  • C polycarbonate diol compound
  • the chipping resistance is sometimes reduced since the intermediate coated film has a rigidity, and further enhancement of the chipping resistance is needed.
  • the chipping resistance may be insufficient due to the rigidity of the intermediate coated film.
  • an adhesive layer is usually formed on the top coated film, and a member, for example, a glass member such as front glass or rear glass, is fixed onto the multilayer coated film through the adhesive layer, but when, for example, the intermediate coated film is softened with the intention to enhance the chipping resistance, the multilayer coated film below the adhesive layer may cause cohesion failure, or separation may occur between an electrodeposition coated film and the intermediate coated film, resulting in defective bonding to the member.
  • a member for example, a glass member such as front glass or rear glass
  • the clear coating composition containing the hydroxyl group-containing acrylic resin and the polyisocyanate compound is used in the usual method of forming a multilayer coated film by the aqueous 3 Wet system, the polyisocyanate compound permeates the base coated film and the intermediate coated film, and the physical properties thereof may be changed, resulting in decrease in scratch resistance and coated film hardness.
  • an object in an aspect of the present invention is to provide a method for forming a multilayer coated film, ensuring that in the method of forming a multilayer coated film by the aqueous 3 Wet system, even when an alloyed hot-dip galvanized steel plate is used as the steel plate, a multilayer coated film having more excellent chipping resistance than ever before and also having excellent adhesion strength for bonding to a member such as glass member, scratch resistance and coated film hardness can be formed.
  • aqueous intermediate coating composition including sequentially applying an aqueous intermediate coating composition, an aqueous base coating composition, and a clear coating composition on/above an electrodeposition-coated alloyed hot-dip galvanized steel plate, thereby forming a multilayer coated film composed of an intermediate coated film, a base coated film and a clear coated film, when the aqueous intermediate coating composition use the coating composition which contains a hydroxyl group-containing acrylic resin (a1) having a glass transition temperature in a specific range and a weight average molecular weight in a specific range, a polyurethane resin (a2) having a glass transition temperature in a specific range, a hydroxyl group-containing polyester resin (a3), a melamine resin (a4), and an active methylene-blocked polyisocyanate compound (a5) and when the ratio of the hydroxyl group-containing acrylic resin (a1) to the polyurethane resin (a2) in the
  • the present invention provides the following method.
  • a method for forming a multilayer coated film on an electrodeposition-coated alloyed hot-dip galvanized steel plate comprising the following steps (1) to (4):
  • step (1) applying an aqueous intermediate coating composition (A) to an electrodeposition coated film, thereby forming an intermediate coated film on the electrodeposition coated film;
  • step (2) after preheating, applying an aqueous base coating composition (B) to the intermediate coated film, thereby forming a base coated film on the intermediate coated film;
  • step (3) after preheating, applying a clear coating composition (C) to the base coated film, thereby forming a clear coated film on the base coated film;
  • step (4) heat-curing the intermediate coated film formed in the step (1), the base coated film formed in the step (2) and the clear coated film formed in the step (3),
  • the aqueous intermediate coating composition (A) contains a hydroxyl group-containing acrylic resin (a1) having a glass transition temperature (Tg) of 5 to 15° C. and a weight average molecular weight of 30,000 to 40,000, a polyurethane resin (a2) having a glass transition temperature (Tg) of ⁇ 50° C.
  • a ratio of the hydroxyl group-containing acrylic resin (a1) to the polyurethane resin (a2) is from 20/10 to 30/10 in terms of solid content ratio
  • the heat-cured coated film of the aqueous intermediate coating composition (A) has an elongation at break at 20° C. of 20 to 30%, a Young's modulus of 5,000 to 6,000 kgf/cm 2 , and a Tukon hardness of 4 to 6, and
  • the clear coating composition (C) contains a hydroxyl group-containing acrylic resin (c1) and an allophanate group-containing polyisocyanate compound (c2).
  • the aqueous intermediate coating composition contains a hydroxyl group-containing acrylic resin (a1) having a glass transition temperature in a specific range and a weight average molecular weight in a specific range, a polyurethane resin (a2) having a glass transition temperature in a specific range, a hydroxyl group-containing polyester resin (a3), a melamine resin (a4), and an active methylene-blocked polyisocyanate compound (a5), the ratio of the hydroxyl group-containing acrylic resin (a1) to the polyurethane resin (a2) in the aqueous intermediate coating composition is controlled to a specific range, and the elongation at break, Young's modulus and Tukon hardness of the coated film formed are controlled to specific ranges, respectively, and the clear coating composition contains the hydroxyl group-containing acrylic resin (c1) and the allophanate group-containing polyisocyanate compound (c2) in the method of forming a multilayer coated film by the aqueous intermediate coating composition.
  • the multilayer coated film can have more excellent chipping resistance than ever before, and the adhesion strength for bonding of a member can be enhanced, and a coated film having excellent scratch resistance and coated film hardness can be formed.
  • the multifunctional and high viscosity (high molecular weight) allophanate group-containing polyisocyanate compound is used in the clear coating composition, resulting in a possibility of controlling the permeation of the polyisocyanate compound to the base coated film and the intermediate coated film, and according to this, the excellent scratch resistance and coated film hardness can be realized.
  • the method includes the following steps (1) to (4):
  • step (1) applying an aqueous intermediate coating composition (A) to an electrodeposition coated film, thereby forming an intermediate coated film on the electrodeposition coated film;
  • step (2) after preheating the intermediate coated film formed in the step (1), applying an aqueous base coating composition (B) to the intermediate coated film, thereby forming a base coated film on the intermediate coated film;
  • step (3) after preheating the base coated film formed in the step (2), applying a clear coating composition (C) to the base coated film, thereby forming a clear coated film on the base coated film; and
  • step (4) heat-curing the intermediate coated film formed in the step (1), the base coated film formed in the step (2) and the clear coated film formed in the step (3).
  • step (5) a step of forming an adhesive layer on the clear coated film may be provided as step (5).
  • the material to be coated to which the method for forming a multilayer coated film is applied is an electrodeposition-coated alloyed hot-dip galvanized steel plate and is usually used for an automotive body.
  • a material of the automotive body may be appropriately subjected to a conventional surface treatment.
  • the electrodeposition coating composition that may be used for electrodeposition coating may be either a cationic resin-based composition or an anionic resin-based composition and may be either a water-soluble composition or a water-dispersible composition, and a coating composition known per se may be used.
  • a cationic resin-based composition is usually used, and a cationic electrodeposition coating composition containing a cationic resin may be suitably used.
  • the cationic electrodeposition coating composition include a cationic electrodeposition coating composition containing a cationic base resin having a cationic group and a crosslinking functional group such as hydroxyl group, carboxyl group and amino group (e.g., an epoxy resin, an acrylic resin, a polybutadiene resin, each modified with an amino group-containing compound), and a crosslinking agent such as blocked polyisocyanate compound, epoxy resin and melamine resin.
  • a cationic electrodeposition coating composition containing a cationic base resin having a cationic group and a crosslinking functional group such as hydroxyl group, carboxyl group and amino group (e.g., an epoxy resin, an acrylic resin, a polybutadiene resin, each modified with an amino group-containing compound), and a crosslinking agent such as blocked polyisocyanate compound, epoxy resin and melamine resin.
  • a neutralizer for the base resin a color pigment, an anticorrosive pigment, an extender pigment, a hydrophilic organic solvent, etc. are usually further blended, if desired.
  • the electrodeposition coating composition can be applied by an ordinary method depending on an electrodeposition coating composition to be used.
  • electrodeposition coating may be performed in a usual manner, for example, by diluting the coating composition with deionized water to a solids mass concentration of preferably about 5 mass % to about 40 mass % and keeping the pH usually at 5.5 to 8.0.
  • the coated film may be heat-cured at a temperature of usually about 140° C. to about 210° C., preferably at a temperature of 150° C. to 180° C., for usually 10 minutes to 60 minutes, preferably for 20 minutes to 30 minutes.
  • the thickness of the coated film is preferably from about 10 ⁇ m to about 60 ⁇ m, particularly preferably from 15 ⁇ m to 30 ⁇ m, based on the cured coated film.
  • an aqueous intermediate coating composition (A) is applied onto an electrodeposition coated film of an electrodeposition-coated alloyed hot-dip galvanized steel plate to form an intermediate coated film.
  • the intermediate coating composition is applied for the purpose of forming an intermediate coated film layer between an undercoat film and a top coated film to contribute to enhancement of adhesion among layers of the multilayer coated film and covering the roughness on a surface of a material to be coated to improve finish appearance, chipping resistance, etc.
  • the aqueous intermediate coating composition (A) contains a hydroxyl group-containing acrylic resin (a1), a polyurethane resin (a2), a hydroxyl group-containing polyester resin (a3), a melamine resin (a4), and an active methylene-blocked polyisocyanate compound (a5), and additionally contains, if desired, a pigment (F) and an organic solvent (G).
  • the hydroxyl group-containing acrylic resin (a1) can be produced, for example, by (co)polymerizing at least one unsaturated monomer component having a hydroxyl group-containing unsaturated monomer and, depending on the case, further having other unsaturated monomer(s) copolymerizable with the monomer above, under normal conditions.
  • the hydroxyl group-containing unsaturated monomer is a compound having at least one hydroxyl group and at least one polymerizable unsaturated bond per molecule, and examples thereof include a monoesterified product of a (meth)acrylic acid with a dihydric alcohol having a carbon number of 2 to 8, such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate and 4-hydroxybutyl (meth)acrylate; an ⁇ -caprolactone-modified monoesterified product of a (meth)acrylic acid and a dihydric alcohol having a carbon number of 2 to 8; an allyl alcohol; and a (meth)acrylate having a polyoxyethylene chain having a hydroxyl group at a molecular terminal.
  • a monoesterified product of a (meth)acrylic acid with a dihydric alcohol having a carbon number of 2 to 8 such as 2-hydroxyethyl (meth
  • (meth)acrylate is a generic term of acrylate and methacrylate
  • (meth)acrylic acid is a generic term of acrylic acid and methacrylic acid.
  • Examples of the other unsaturated monomer(s) copolymerizable with the above-described hydroxyl group-containing unsaturated monomer include an alkyl (meth)acrylate or cycloalkyl (meth)acrylate, such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, i-propyl (meth)acrylate, n-butyl (meth)acrylate, i-butyl (meth)acrylate, tert-butyl (meth)acrylate, n-hexyl(meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, tridecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, “Isostearyl Acrylate” (trade name, produced by Os
  • the hydroxyl group-containing acrylic resin (a1) has a glass transition temperature (Tg) of from 5 to 15° C. When Tg falls within the range above, the chipping resistance can be enhanced.
  • the glass transition temperature Tg of the hydroxy group-containing acrylic resin is a value calculated in accordance with the following formula:
  • Tg (° C.) Tg ( K ) ⁇ 273
  • W1, W2, . . . Wn are mass fractions of respective monomers
  • T1, T2 . . . . Tn are glass transition temperatures Tg (K) of homopolymers of respective monomers.
  • the glass transition temperature of a homopolymer of each monomer is a value from POLYMER HANDBOOK, Fourth Edition, compiled by J. Brandrup, E. H. Immergut, and E. A. Grulke (1999), and as for the glass transition temperature of a monomer not described in the document, a value obtained by synthesizing a homopolymer of the monomer to have a weight average molecular weight of about 50,000 and measuring the glass transition temperature thereof by differential scanning thermal analysis is used.
  • the hydroxyl group-containing acrylic resin (a1) has a weight average molecular weight of from 30,000 to 40,000. When the weight average molecular weight falls within the range above, the chipping resistance can be enhanced.
  • the hydroxyl group-containing acrylic resin (a1) may have a hydroxyl value of usually from 1 to 200 mgKOH/g, preferably from 2 to 100 mgKOH/g, more preferably from 3 to 60 mgKOH/g, and an acid value of usually from 1 to 200 mgKOH/g, preferably from 2 to 150 mgKOH/g, more preferably from 5 to 100 mgKOH/g.
  • the hydroxyl value (mgKOH/g) of the resin is expressed by the number of mg of potassium hydroxide equivalent to the hydroxyl content of 1 g of the resin.
  • a molecular weight of potassium hydroxide is 56.1.
  • the acid value (mgKOH/g) of the resin is expressed by the number of mg of potassium hydroxide equivalent to the acid content of 1 g of the resin.
  • the molecular weight of potassium hydroxide is 56.1.
  • the polyurethane resin (a2) has a glass transition temperature (Tg) of ⁇ 50° C. or less and has a polyether skeleton.
  • Tg glass transition temperature
  • Preferable examples of the polyurethane resin (a2) include the following urethane resin emulsion (a2-i).
  • urethane resin emulsion (a2-i) examples include a urethane resin emulsion produced from a polyisocyanate component (a2-i-1) and a polyol component (a2-i-2) in accordance with a conventional method.
  • polyisocyanate component (a2-i-1) examples include diisocyanate and other polyisocyanates.
  • the diisocyanate as a raw material of the urethane resin emulsion (a2-i) is not particularly limited, and one kind of or a mixture of two or more kinds of diisocyanates widely used in this technical field may be used.
  • the diisocyanate include an aromatic diisocyanate such as tolylene diisocyanate, diphenylmethane-4,4′-diisocyanate, p-phenylene diisocyanate, xylylene diisocyanate, 1,5-naphthylene diisocyanate, 3,3′-dimethyldiphenyl-4,4′-diisocyanate, dianisidine diisocyanate and tetramethylxylylene diisocyanate; an alicyclic diisocyanate such as isophorone diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, trans-1,4-cyclohexyl diisocyanate and
  • the diisocyanate above may be used in the form of a blocked isocyanate blocked with various blocking agents.
  • the content (mass %) of diisocyanate in the polyisocyanate component (a2-i-1) is preferably from 10 to 60%, more preferably from 20 to 40%, from the viewpoint of chipping resistance.
  • Another polyisocyanate as a raw material of the urethane resin emulsion (a2-i) is a polyisocyanate having three or more isocyanate group per molecule.
  • examples thereof include isocyanurate trimer, biuret trimer, and trimethylolpropane adduct of the above-exemplified diisocyanates; and a trifunctional or higher functional isocyanate such as triphenylmethane triisocyanate, 1-methylbenzole-2,4,6-triisocyanate and dimethyltriphenylmethane tetraisocyanate, and such an isocyanate compound may be used in the form of a product modified by carbodiimide, isocyanurate, biuret, etc. or may be used in the form of a blocked isocyanate blocked with various blocking agents.
  • Examples of the polyol component (a2-i-2) include a polyol having a polyether skeleton that imparts a polyether skeleton to the polyurethane resin (a2).
  • Examples of such a polyol include a polyoxyalkylene glycol such as polyethylene glycol, polypropylene glycol, poly(ethylene)propylene glycol and polytetramethylene glycol; and an ethylene oxide and/or propylene oxide adduct of a polyhydric alcohol.
  • polyhydric alcohol examples include aliphatic diols such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,4-butanediol, neopentyl glycol, 3-methyl-2,4-pentanediol, 2,4-pentanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 2-methyl-2,4-pentanediol, 2,4-diethyl-1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 3,5-heptanediol, 1,8-octanediol, 2-methyl-1,8-octanediol, 1,9
  • the ratio of the polyisocyanate component (a2-i-1) to the polyol component (a2-i-2) is not particularly limited, but in a preferred embodiment, the polyol component (a2-i-2) is used in a ratio of preferably from 40 to 90 mass %, more preferably from 50 to 80 mass %, relative to total mass of the polyisocyanate component (a2-i-1) and the polyol component (a2-i-2) used for the production of the urethane resin emulsion (a2-i).
  • an amine component (a2-i-3) may be used as a raw material in order to, e.g., form a urea bond or achieve a high molecular weight.
  • examples of the amine component (a2-i-3) include a monoamine compound and a diamine compound.
  • the monoamine compound is not particularly limited, and one kind of or a mixture of two or more kinds of monoamine compounds widely used in this technical filed may be used.
  • the monoamine compound include an alkylamine such as ethylamine, propylamine, 2-propylamine, butylamine, 2-butylamine, tertiary-butylamine and isobutylamine; an aromatic amine such as aniline, methylaniline, phenylnaphthylamine and naphthylamine; an alicyclic amine such as cyclohexaneamine and methylcyclohexaneamine; an ether amine such as 2-methoxyethylamine, 3-methoxypropylamine and 2-(2-methoxyethoxy)ethylamine; and an alkanolamine such as ethanolamine, propanolamine, butylethanolamine, 1-amino-2-methyl-2-propanol, 2-amino-2-methylpropanol, diethanol
  • the diamine compound is not particularly limited, and one kind of or a mixture of two or more kinds of diamine compounds widely used in this technical field may be used.
  • the diamine compound include low molecular diamines obtained by substituting an alcoholic hydroxyl group of the above-exemplified low molecular diols with an amino group, such as ethylenediamine and propylenediamine; polyether diamines such as polyoxypropylene diamine and polyoxyethylene diamine; alicyclic diamines such as menthenediamine, isophoronediamine, norbornenediamine, bis(4-amino-3-methyldicyclohexyl)methane, diaminodicyclohexylmethane, bis(aminomethyl)cyclohexane and 3,9-bis(3-aminopropyl)2,4,8,10-tetraoxaspiro(5,5)undecane; aromatic diamines such as m-xylenediamine, ⁇ -(m
  • an internal branching agent and an internal crosslinking agent capable of providing a branch and a crosslinked structure to a polyurethane molecule may be used, in addition to the components (a2-i-1) to (a2-i-3).
  • the internal branching agent and internal crosslinking agent examples thereof include trimethylolpropane.
  • the method of producing the urethane resin emulsion (a2-i) is not particularly limited, and a method widely used in this technical field may be used.
  • Preferable examples of the production method include a method of synthesizing a prepolymer or a polymer in a solvent that is inert to the reaction and has high affinity for water, and feeding and dispersing it into water.
  • Examples thereof include (i) a method of synthesizing a prepolymer from the polyisocyanate component (a2-i-1) and the polyol component (a2-i-2) in the solvent above, and reacting it in water with the amine component (a2-i-3) that is used, if desired; and (ii) a method of synthesizing a polymer from the polyisocyanate component (a2-i-1), the polyol component (a2-i-2), and the amine component (a2-i-3) that is used, if desired, and feeding and dispersing it into water.
  • a neutralizer component may be previously added to water into which the prepolymer or polymer is fed, or may be added after feeding.
  • the solvent being inert to the reaction and having high affinity for water
  • examples thereof include acetone, methyl ethyl ketone, dioxane, tetrahydrofuran, and N-methyl-2-pyrrolidone.
  • Such a solvent is usually used in a ratio of 3 to 100 mass % relative to the total amount of those raw materials used for the production of prepolymer.
  • the blending ratio is not particularly limited.
  • the blending ratio may be replaced by the molar ratio in a reaction stage between an isocyanate group in the polyisocyanate component (a2-i-1) and an isocyanate reactive group in the polyol component (a2-i-2) and the amine component (a2-i-3) that is used, if desired.
  • the molar ratio if an unreacted isocyanate group is lack in dispersed polyurethane molecules, adhesiveness of the coated film and/or strength of the coated film may be reduced when the polyurethane resin is used for a coating composition, and if an unreacted isocyanate group is present in an excessive amount, it may affect dispersion stability and/or physical properties of the coating composition.
  • the molar ratio of an isocyanate reactive group is preferably from 0.5 to 2.0 when assuming an isocyanate group is 1.
  • the molar ratio of an isocyanate reactive group in the polyol component (a2-i-2) is preferably from 0.3 to 1.0, more preferably from 0.5 to 0.9, when assuming an isocyanate group in the polyisocyanate component (a2-i-1) is 1.
  • the molar ratio of an isocyanate reactive group in the amine component (a2-i-3) that is used, if desired, is preferably from 0.1 to 1.0, more preferably from 0.2 to 0.5, when assuming an isocyanate group in the polyisocyanate component is 1.
  • one kind of or two or more kinds of emulsifiers such as surfactant may be used.
  • the particle diameter thereof is not particularly limited but is preferably 1 ⁇ m or less, more preferably 500 nm or less, because good dispersion state can be maintained.
  • an anionic surfactant, a nonionic surfactant, a cationic surfactant, an amphoteric surfactant, a high molecular surfactant, a reactive surfactant, etc. which are widely used in this technical field and used in a urethane resin emulsion, may be used.
  • an anionic surfactant, a nonionic surfactant and a cationic surfactant are preferred.
  • anionic surfactant examples include alkyl sulfates such as sodium dodecyl sulfate, potassium dodecyl sulfate and ammonium dodecyl sulfate; sodium dodecyl polyglycol ether sulfate; sodium sulforicinoleate; an alkyl sulfonate such as alkali metal salt of sulfonated paraffin and ammonium salt of sulfonated paraffin; a fatty acid salt such as sodium laurate, triethanolamine oleate and triethanolamine abietate; an alkylaryl sulfonate such as sodium benzene sulfonate and alkali metal sulfate of alkali phenol hydroxyethylene; a higher alkylnaphthalenesulfonate; a naphthalenesulfonic acid-formalin condensate; a dialkylsulfosuccinate; a polyoxy
  • nonionic surfactant examples include an ethylene oxide and/or propylene oxide adduct of an alcohol having a carbon number of 1 to 18, an ethylene oxide and/or propylene oxide adduct of an alkylphenol, and an ethylene oxide and/or propylene oxide adduct of an alkylene glycol and/or an alkylene diamine.
  • examples thereof include methanol, ethanol, propanol, 2-propanol, butanol, 2-butanol, tertiary-butanol, amyl alcohol, isoamyl alcohol, tertiary-amyl alcohol, hexanol, octanol, decane alcohol, lauryl alcohol, myristyl alcohol, palmityl alcohol, and stearyl alcohol.
  • alkylphenols examples include phenol, methylphenol, 2,4-di-tertiary-butylphenol, 2,5-di-tertiary-butylphenol, 3,5-di-tertiary-butylphenol, 4-(1,3-tetramethylbutyl)phenol, 4-isooctylphenol, 4-nonylphenol, 4-tertiary-octylphenol, 4-dodecylphenol, 2-(3,5-dimethylheptyl)phenol, 4-(3,5-dimethylheptyl)phenol, naphthol, bisphenol A, and bisphenol F.
  • alkylene glycol examples include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, and 1,6-hexanediol.
  • alkylene diamine examples include these alkylene glycols in which an alcoholic hydroxy group is substituted with an amino group.
  • the ethylene oxide and propylene oxide adducts may be a random adduct or a block adduct.
  • cationic surfactant examples include primary to tertiary amine salts, a pyridinium salt, an alkyl pyridinium salt, and a quaternary ammonium salt such as alkyl halide quaternary ammonium salt.
  • the amount thereof is not particularly limited, and the emulsifier may be used in any amount, but when the amount used is 0.01 or more in terms of mass ratio when assuming the urethane resin is 1, sufficient dispersibility is obtained, and when the molar ratio is 0.3 or less when assuming the urethane resin is 1, reduction in the physical properties such as water resistance, strength and elongation of the coated film, etc. obtained from an aqueous first colored coating composition can be prevented.
  • urethane resin emulsion (a2-i) a commercial product may be used.
  • the commercial product include “Bayhydrol” series produced by Covestro; “Superflex” (registered trademark) series produced by Dai-Ichi Kogyo Seiyaku Co., Ltd.); and “PERMARIN” (registered trademark) series and “UCOAT” (registered trademark) series produced by Sanyo Chemical Industries, Ltd.
  • the solid content thereof is not particularly limited, and any value may be selected.
  • the solid content is preferably from 10 to 50 mass % because of good dispersibility and coating performance, and more preferably from 20 to 40 mass %.
  • the average molecular weight of the urethane resin dispersed in the urethane resin emulsion (a2-i) is not particularly limited, and any range, in which dispersibility as an aqueous coating composition is imparted and a good coated film is formed, may be selected.
  • the weight average molecular weight is preferably from 1,000 to 500,000, more preferably from 5,000 to 200,000.
  • the hydroxyl value is also not particularly limited, and any value may be selected.
  • the acid value is expressed in consumption (mg) of KOH per gram of resin and is usually from 0 to 100 mgKOH/g.
  • the glass transition temperature (Tg) of the urethane resin dispersed in the urethane resin emulsion (a2-i) is ⁇ 50° C. or less. When Tg falls within this range, the chipping resistance can be enhanced. Tg is preferably from ⁇ 80 to ⁇ 50° C., more preferably from ⁇ 75 to ⁇ 50° C.
  • the glass transition temperature (Tg) of the urethane resin above is a value measured using a dynamic viscoelasticity measuring apparatus and can be a value in the catalogue of the raw material manufacturer.
  • the hydroxyl group-containing polyester resin (a3) can be synthesized by a known method of subjecting a polybasic acid and a polyhydric alcohol to an esterification reaction in a usual manner.
  • the hydroxyl group-containing polyester resin (a3) preferably has an acid group such as carboxyl group.
  • the polybasic acid is a compound having two or more carboxyl groups per molecule and examples thereof include phthalic acid, isophthalic acid, terephthalic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, naphthalenedicarboxylic acid, 4,4-diphenyldicarboxylic acid, diphenylmethane-4,4′-dicarboxylic acid, HET acid, maleic acid, fumaric acid, itaconic acid, trimellitic acid, pyromellitic acid, cyclohexane-1,3-dicarboxylic acid, cyclohexane-1,4-dicarboxylic acid, hexahydrophthalic acid, hexahydroisophthalic acid, hexahydroterephthalic acid, tetrahydrophthalic acid, hexahydrotrimellitic acid, methylhexahydrophthalic acid, and anhydrides thereof.
  • the polyhydric alcohol is a compound having two or more hydroxyl groups per molecule and examples thereof include glycols such as ethylene glycol, propylene glycol, diethylene glycol, trimethylene glycol, tetraethylene glycol, triethylene glycol, dipropylene glycol, 1,4-butanediol, 1,3-butanediol, 2,3-butanediol, 1,2-butanediol, 3-methyl-1,2-butanediol, 1,2-pentanediol, 1,5-pentanediol, 1,4-pentanediol, 2,4-pentanediol, 2,3-dimethyltrimethylene glycol, tetramethylene glycol, 3-methyl-4,5-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 1,6-hexanediol, 1,5-hexanediol, 1,4-hex
  • a fatty acid-modified polyester resin modified with, e.g., a (semi)drying oil fatty acid such as linseed oil fatty acid, coconut oil fatty acid, safflower oil fatty acid, soybean oil fatty acid, sesame oil fatty acid, perilla oil fatty acid, hempseed oil fatty acid, tall oil fatty acid and dehydrated castor oil fatty acid, may also be used.
  • a (semi)drying oil fatty acid such as linseed oil fatty acid, coconut oil fatty acid, safflower oil fatty acid, soybean oil fatty acid, sesame oil fatty acid, perilla oil fatty acid, hempseed oil fatty acid, tall oil fatty acid and dehydrated castor oil fatty acid
  • the modification amount with such a fatty acid is suitably 30 mass % or less in terms of oil length.
  • the hydroxyl group-containing polyester resin (a3) may be a resin in which a part of a monobasic
  • the hydroxyl group-containing polyester resin (a3) may also be a resin in which an ⁇ -olefin epoxide such as propylene oxide or butylene oxide, a monoepoxy compound such as CARDURA E10 (produced by Momentive Specialty Chemicals Inc., trade name, a glycidyl ester of a synthetic hyperbranched saturated fatty acid), etc. is reacted with an acid group in the polyester resin.
  • an ⁇ -olefin epoxide such as propylene oxide or butylene oxide
  • a monoepoxy compound such as CARDURA E10 (produced by Momentive Specialty Chemicals Inc., trade name, a glycidyl ester of a synthetic hyperbranched saturated fatty acid), etc.
  • the carboxyl group may be introduced, for example, by adding an acid anhydride to a hydroxyl group-containing polyester resin to cause half-esterification.
  • the hydroxyl value of the hydroxyl group-containing polyester resin (a3) is preferably from 10 mg KOH/g to 250 mg KOH/g, particularly preferably from 40 mg KOH/g to 170 mg KOH/g, from the viewpoint of finish appearance and curability of the coated film.
  • the acid value is preferably from 1 mg KOH/g to 100 mg KOH/g, particularly preferably from 5 mg KOH/g to 60 mg KOH/g, from the viewpoint of curability and adhesion of the coated film.
  • the number average molecular weight of the hydroxyl group-containing polyester resin (a3) is preferably from 1,000 to 50,000, particularly preferably from 1,000 to 10,000, from the viewpoint of curability and finish appearance of the coated film.
  • the number average molecular weight of the hydroxyl group-containing polyester resin (a3) is determined by gel permeation chromatograph (GPC).
  • a melamine resin (a4) is contained as an aqueous crosslinking agent component of the intermediate coating composition (A).
  • melamine resin examples thereof include a partially methylolated melamine resin or a fully methylolated melamine resin, obtained by the reaction of a melamine component and an aldehyde component.
  • aldehyde component examples include formaldehyde, paraformaldehyde, acetaldehyde, benzaldehyde, etc.
  • a methylolated melamine resin in which the methylol group is etherified in part or in whole with an appropriate alcohol may also be used.
  • the alcohol to be used for the etherification include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, 2-ethyl-1-butanol, and 2-ethyl-1-hexanol.
  • the melamine resin is preferably a methyl-etherified melamine resin obtained by etherifying, in part or in whole, the methylol group of a partially or fully methylolated melamine resin with methyl alcohol, a butyl-etherified melamine resin obtained by etherifying, in part or in whole, the methylol group of a partially or fully methylolated melamine resin with butyl alcohol, or a methyl-butyl mixture-etherified melamine resin obtained by etherifying, in part or in whole, the methylol group of a partially or fully methylolated melamine resin with methyl alcohol and butyl alcohol, more preferably a methyl-butyl mixture-etherified melamine resin.
  • the weight average molecular weight of the melamine resin is preferably from 400 to 6,000, more preferably from 500 to 4,000, still more preferably from 600 to 3,000.
  • a commercially available melamine resin can be used as the melamine resin.
  • examples thereof include “CYMEL 202”, “CYMEL 203”, “CYMEL 204”, “CYMEL 211”, “CYMEL 212”, “CYMEL 238”, “CYMEL 251”, “CYMEL 253”, “CYMEL 254”, “CYMEL 303”, “CYMEL 323”, “CYMEL 324”, “CYMEL 325”, “CYMEL 327”, “CYMEL 350”, “CYMEL 370”, “CYMEL 380”, “CYMEL 385”, “CYMEL 1156”, “CYMEL 1158”, “CYMEL 1116”, and “CYMEL 1130” (trade names, all produced by Allnex Japan Inc., CYMEL is a registered trademark); “RESIMENE 735”, “RESIMENE 740”, “RESIMENE 741”, “RESIMENE 745”, “RESIMENE 746”, and “RESIMENE 747
  • Examples of the active methylene-blocked polyisocyanate compound (a5) include a blocked polyisocyanate compound obtained by reacting an active methylene compound with an isocyanate group in a polyisocyanate compound.
  • An active methylene-blocked polyisocyanate compound (a5-i) having a hydrophilic group is particularly preferred.
  • a blocked polyisocyanate compound (a5-i-3) obtained by reacting an active hydrogen-containing compound having a hydrophilic group with a part of isocyanate groups in a polyisocyanate compound (a5-i-1) to introduce the hydrophilic group, and further reacting an active methylene compound (a5-i-2) with an isocyanate group in the polyisocyanate compound (a5-i-1) may be preferably used.
  • a compound obtained by reacting a secondary alcohol (a5-i-4) having a carbon number of 6 or more with the blocked polyisocyanate compound (a5-i-3) may be preferably used.
  • the polyisocyanate compound (a5-i-1) has at least two isocyanate groups per molecule and examples thereof include an aliphatic polyisocyanate, an alicyclic polyisocyanate, an aromatic-aliphatic polyisocyanate, an aromatic polyisocyanate, and derivatives of these polyisocyanates.
  • aliphatic polyisocyanate examples include an aliphatic diisocyanate such as trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, dimer acid diisocyanate and methyl 2,6-diisocyanatohexanoate (common name: lysine diisocyanate); and an aliphatic triisocyanate such as 2-isocyanatoethyl 2,6-diisocyanatohexanoate, 1,6-diisocyanato-3-isocyanatomethylhexane, 1,4,8-triisocyanatooctane, 1,6,11
  • alicyclic polyisocyanate examples include an alicyclic diisocyanate such as 1,3-cyclopentene diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (common name: isophorone diisocyanate), 4-methyl-1,3-cyclohexylene diisocyanate (common name: hydrogenated TDI), 2-methyl-1,3-cyclohexylene diisocyanate, 1,3- or 1,4-bis(isocyanatomethyl)cyclohexane (common name: hydrogenated xylylene diisocyanate) or a mixture thereof, methylenebis(4,1-cyclohexanediyl) diisocyanate (common name: hydrogenated MDI) and norbornane diisocyanate; and an alicyclic triisocyanate
  • aromatic-aliphatic polyisocyanate examples include an aromatic-aliphatic diisocyanate such as methylenebis(4,1-phenylene)diisocyanate (common name: MDI), 1,3- or 1,4-xylylene diisocyanate or a mixture thereof, ⁇ , ⁇ ′-diisocyanato-1,4-diethylbenzene, and 1,3- or 1,4-bis(1-isocyanato-1-methylethyl)benzene (common name: tetramethylxylylene diisocyanate) or a mixture thereof; and an aromatic-aliphatic triisocyanate such as 1,3,5-triisocyanatomethylbenzene.
  • aromatic-aliphatic diisocyanate such as methylenebis(4,1-phenylene)diisocyanate (common name: MDI), 1,3- or 1,4-xylylene diisocyanate or a mixture thereof, ⁇ , ⁇ ′-diisocyan
  • aromatic polyisocyanate examples include an aromatic diisocyanate such as m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4′-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 2,4-tolylene diisocyanate (common name: 2,4-TDI) or 2,6-tolylene diisocyanate (common name: 2,6-TDI) or a mixture thereof, 4,4′-toluidine diisocyanate and 4,4′-diphenylether diisocyanate; an aromatic triisocyanate such as triphenylmethane-4,4′,4′′-triisocyanate, 1,3,5-triisocyanatobenzene and 2,4,6-triisocyanatotoluene; and an aromatic tetraisocyanate such as 4,4′-diphenylmethane-2,2′,5,5′-tetraisocyanate.
  • Examples of the derivative of the polyisocyanate include a dimer, a trimer, a biuret, an allophanate, a urethodione, a urethoimine, an isocyanurate, an oxadiazinetrione, a polymethylene polyphenyl polyisocyanate (crude MDI; polymeric MDI), and a crude TDI, of the above-described polyisocyanate.
  • polyisocyanates and derivatives thereof may be used alone, or two or more thereof may be used in combination.
  • polyisocyanates an aliphatic diisocyanate, an alicyclic diisocyanate, and a derivative thereof are preferred as the polyisocyanate compound (a5-i-1), because yellowing is less likely to occur during heating of the obtained blocked polyisocyanate compound (a5-i-1).
  • an aliphatic diisocyanate and a derivative thereof are more preferred.
  • the active hydrogen-containing compound having a hydrophilic group examples thereof include an active hydrogen-containing compound having a nonionic hydrophilic group, an active hydrogen-containing compound having an anionic hydrophilic group, and an active hydrogen-containing compound having a cationic hydrophilic group, and one of these may be used alone, or two or more thereof may be used in combination.
  • an active hydrogen-containing compound having a nonionic hydrophilic group is preferably used, because the reaction of blocking an isocyanate group in the polyisocyanate compound (a5-i-1) by the active methylene compound (a5-i-2) is less likely to be inhibited.
  • an active hydrogen-containing compound having a nonionic hydrophilic group for example, an active hydrogen-containing compound having a polyoxyalkylene group is preferred.
  • the polyoxyalkylene group include a polyoxyethylene group and a polyoxypropylene group, and one of these may be used alone, or two or more thereof may be used in combination. Among these, from the viewpoint of storage stability of the coating composition, an active hydrogen-containing compound having a polyoxyethylene group is preferred.
  • the active hydrogen-containing compound having a polyoxyethylene group preferably contains 3 or more continuous oxyethylene groups, more preferably from 5 to 100 continuous oxyethylene groups, still more preferably from 8 to 45 continuous oxyethylene groups.
  • the active hydrogen-containing compound having a polyoxyethylene group may contain an oxyalkylene group except for an oxyethylene group, in addition to the continuous oxyethylene groups.
  • the oxyalkylene group except for the oxyethylene group examples thereof include an oxypropylene group, an oxybutylene group, and an oxystyrene group.
  • the molar ratio of the oxyethylene group in the oxyalkylene group is preferably from 20 to 100 mol %, more preferably from 50 to 100 mol %. When the molar ratio of the oxyethylene group in the oxyalkylene group is 20 mol % or more, sufficient hydrophilicity can be imparted and therefore, reduction in the storage stability of the coating composition can be prevented.
  • the number average molecular weight is preferably from 200 to 2,000.
  • the lower limit of the number average molecular weight is preferably 300, more preferably 400.
  • the upper limit is preferably 1,500, more preferably 1,200.
  • examples thereof include a polyethylene glycol monoalkyl ether (another name: ⁇ -alkoxy polyoxyethylene) such as polyethylene glycol monomethyl ether and polyethylene glycol monoethyl ether; a polypropylene glycol monoalkyl ether (another name: ⁇ -alkoxy polyoxypropylene) such as polypropylene glycol monomethyl ether and polypropylene glycol monoethyl ether; an ⁇ -alkoxy polyoxyethylene (oxypropylene) such as ⁇ -methoxy polyoxyethylene (oxypropylene) and ⁇ -ethoxy polyoxyethylene (oxypropylene); a polyethylene glycol (propylene glycol) monoalkyl ether such as polyethylene glycol (propylene glycol) monomethyl ether and polyethylene glycol (propylene glycol) monoethyl ether; and polyethylene glycol, polypropylene glycol, polyethylene glycol (propylene glycol, polyethylene glycol (propylene glycol), polyethylene glyco
  • Examples of the commercial product of the polyethylene glycol monomethyl ether examples thereof include “Uniox M-400”, “Uniox M-550”, “Uniox M-1000”, and “Uniox M-2000” (trade names, all produced by NOF Corporation, Uniox is a registered trademark).
  • Examples of the commercial product of the polyethylene glycol include “PEG #200”, “PEG #300”, “PEG #400”, “PEG #600”, “PEG #1000”, “PEG #1500”, “PEG #1540”, and “PEG #2000” (trade names, all produced by NOF Corporation).
  • the reaction of a part of isocyanate groups in the polyisocyanate compound (a5-i-1) with the active hydrogen-containing compound having a hydrophilic group can be performed at 0 to 150° C., and a solvent may be used.
  • the solvent is preferably an aprotic solvent and is particularly preferably an ester, an ether, an N-alkylamide, a ketone, etc.
  • the active hydrogen-containing compound which has not reacted with an isocyanate group in the polyisocyanate compound (a5-i-1) can be removed after the completion of reaction.
  • the number of moles of the active hydrogen in the active hydrogen-containing compound is preferably from 0.03 to 0.6 mol, more preferably from 0.04 to 0.4 mol, per mol of the isocyanate group in the polyisocyanate compound (a5-i-1).
  • Examples of the active methylene compound (a5-i-2) include a malonic acid diester such as dimethyl malonate, diethyl malonate, di-n-propyl malonate, diisopropyl malonate, di-n-butyl malonate, diisobutyl malonate, di-sec-butyl malonate, di-tert-butyl malonate, di-n-pentyl malonate, di-n-hexyl malonate, di(2-ethylhexyl) malonate, methyl isopropyl malonate, ethyl isopropyl malonate, methyl n-butyl malonate, ethyl n-butyl malonate, methyl isobutyl malonate, ethyl isobutyl malonate, methyl sec-butyl malonate, ethyl sec-butyl malonate, diphenyl malonate and
  • the active methylene compound (a5-i-2) is preferably at least one compound selected from the group consisting of dimethyl malonate, diethyl malonate, diisopropyl malonate, methyl acetoacetate, ethyl acetoacetate, methyl isobutyrylacetate and ethyl isobutyrylacetate, and more preferably at least one compound selected from the group consisting of diisopropyl malonate, methyl isobutyrylacetate and ethyl isobutyrylacetate.
  • the compound is still more preferably diisopropyl malonate.
  • a reaction catalyst may be used, if desired.
  • the reaction catalyst include a basic compound such as metal hydroxide, metal alkoxide, metal carboxylate, metal acetylacetonate, hydroxide of an onium salt, onium carboxylate, metal salt of an active methylene compound, onium salt of an active methylene compound, aminosilanes, amines and phosphines.
  • an ammonium salt, a phosphonium salt, and a sulfonium salt are preferred.
  • the amount of the reaction catalyst used is preferably from 10 to 10,000 ppm, more preferably from 20 to 5,000 ppm, based on the total solid mass of the polyisocyanate compound (a5-i-1) and the active methylene compound (a5-i-2).
  • the reaction of blocking an isocyanate group by the active methylene compound (a5-i-2) can be performed at 0 to 150° C., and a solvent may be used.
  • the solvent is preferably an aprotic solvent, more preferably an ester, an ether, an N-alkylamide, a ketone, etc.
  • the reaction may be terminated by adding an acid component to neutralize the basic compound as a catalyst.
  • the amount of the active methylene compound (a5-i-2) used is not particularly limited, but is preferably from 0.1 to 3 mol, more preferably from 0.2 to 2 mol, per mol of the isocyanate group in the polyisocyanate compound (a5-i-1).
  • the active methylene compound which has not been reacted with an isocyanate group in the polyisocyanate compound (a5-i-1) can be removed after the completion of blocking reaction.
  • a blocking agent such as alcohol-based blocking agents, phenol-based blocking agents, oxime-based blocking agents, amine-based blocking agents, acid amide-based blocking agents, imidazole-based blocking agents, pyridine-based blocking agents and mercaptan-based blocking agents may be used in combination.
  • an isocyanate group in the polyisocyanate compound (a5-i-1) is reacted with the active methylene compound (a5-i-2) to obtain a blocked polyisocyanate compound (a5-i-3).
  • the blocked polyisocyanate compound (a5-i-3) may be further reacted with a secondary alcohol (a5-i-4) having a carbon number of 6 or more.
  • examples thereof include 4-methyl-2-pentanol, 5-methyl-2-hexanol, 6-methyl-2-heptanol, and 7-methyl-2-octanol. One of these may be used alone, or two or more thereof may be used in combination.
  • the reaction of the blocked polyisocyanate compound (a5-i-3) and the secondary alcohol (a5-i-4) is preferably performed by a method of removing a part or all of the alcohol derived from active methylene in the blocked polyisocyanate compound (a5-i-3) by distillation from the system under heating, reduced pressure, etc., and promoting the reaction.
  • the production method above specifically, it is suitable to remove a part or all of the alcohol at a temperature of usually from 20 to 150° C., preferably from 75 to 95° C., over 5 minutes to 20 hours, preferably over 10 minutes to 10 hours, by reducing the pressure, if desired.
  • the ratio of the secondary alcohol (a5-i-4) is preferably from 5 to 500 parts by mass, more preferably from 10 to 200 parts by mass, based on 100 parts by mass of the solid content of the blocked polyisocyanate compound (a5-i-3).
  • the above-described removing operation may be performed after adding a polyfunctional hydroxy group-containing compound to the blocked polyisocyanate compound (a5-i-3) and the secondary alcohol (a5-i-4).
  • the number average molecular weight of the blocked polyisocyanate compound (a5-i-1) obtained as above is preferably from 600 to 30,000, more preferably from 900 to 10,000.
  • the ratio of the hydroxyl group-containing acrylic resin (a1) to the polyurethane resin (a2) is from 20/10 to 30/10 in terms of solid content ratio. If the ratio of the hydroxyl group-containing acrylic resin (a1) is less than the lower limit above, the chipping resistance and the adhesion to a glass member may deteriorate, whereas if it exceeds the upper limit above, the chipping resistance may deteriorate.
  • the ratio of the components (a1), (a2), (a3), (a4) and (a5) (solid contents) is preferably in the following ranges based on 100 parts by mass of the resin solid content in the aqueous intermediate coating composition (A):
  • hydroxyl group-containing acrylic resin (a1) usually from 5 to 30 parts by mass, preferably from 10 to 30 parts by mass, more preferably from 20 to 30 parts by mass;
  • polyurethane resin (a2) usually from 5 to 20 parts by mass, preferably from 5 to 15 parts by mass, more preferably from 8 to 12 parts by mass;
  • hydroxyl group-containing polyester resin (a3) usually from 10 to 40 parts by mass, preferably from 15 to 35 parts by mass, more preferably from 20 to 30 parts by mass;
  • melamine resin (a4) usually from 10 to 40 parts by mass, preferably from 15 to 35 parts by mass, more preferably from 20 to 30 parts by mass;
  • active methylene-blocked polyisocyanate compound (a5) usually from 5 to 25 parts by mass, preferably from 5 to 15 parts by mass, more preferably from 8 to 12 parts by mass.
  • a pigment usually employed for a coating composition may be used.
  • a color pigment such as titanium dioxide, zinc white, carbon black, phthalocyanine blue, Prussian blue, cobalt blue, azo pigment, phthalocyanine pigment, quinacridone pigment, isoindoline pigment, threne pigment and perylene pigment; an extender pigment such as clay, kaolin, baryta, barium sulfate, barium carbonate, calcium carbonate, silica, alumina white and talc; an effect pigment such as aluminum flake and mica flake; etc. are preferred.
  • the pigment may be blended as a powder in the coating composition, or after the pigment is mixed and dispersed with a part of the resin component to prepare a pigment dispersion in advance, the pigment dispersion may be mixed together with the remaining resin component or other components to form a coating composition.
  • conventional coating composition additives such as antifoaming agent, dispersant and surface regulator may be used, if desired.
  • the pigment above is preferably used as a powder having an average particle diameter of 0.01 ⁇ m to 6 ⁇ m.
  • PWC Porture Weight Content
  • content of the pigment (F) is preferably from 40% to 60%, more preferably from 45% to 55%.
  • Examples of the organic solvent (G) include a hydrocarbon-based solvent such as hexane, heptane, xylene and toluene; esters such as ethyl acetate and butyl acetate; an ether-based solvent such as ethylene glycol monomethyl ether; an alcohol-based solvent such as ethanol, propanol and 2-ethylhexyl alcohol; a ketone-based solvent such as methyl ethyl ketone and methyl isobutyl ketone; an aromatic hydrocarbon-based solvent such as SWASOL 310 and SWASOL 1000 (produced by Cosmo Oil Co., Ltd., SWASOL is a registered trademark); an aliphatic hydrocarbon-based solvent; an alicyclic hydrocarbon-based solvent; and an amide-based solvent.
  • a hydrocarbon-based solvent such as hexane, heptane, xylene and toluene
  • esters such as ethyl acetate and but
  • the content of the organic solvent (G) is usually from 20 mass % to 50 mass %, preferably on the order of 25 mass % to 40 mass %.
  • a curing catalyst may be used from the viewpoint of enhancing the curability.
  • a sulfonic acid such as paratoluenesulfonic acid, dodecylbenzenesulfonic acid and dinonylnaphthalenesulfonic acid; a neutralized salt of the sulfonic acid with amine; a neutralized salt of a phosphoric acid ester compound with amine; etc., may be used.
  • the curing catalyst include an organic metal catalyst such as tin octylate, dibutyltin di(2-ethylhexanoate), dioctyltin di(2-ethylhexanoate), dioctyltin diacetate, dibutyltin dilaurate, dibutyltin oxide, dioctyltin oxide, zinc 2-ethylhexanoate and zinc octylate; and a tertiary amine.
  • organic metal catalyst such as tin octylate, dibutyltin di(2-ethylhexanoate), dioctyltin di(2-ethylhexanoate), dioctyltin diacetate, dibutyltin dilaurate, dibutyltin oxide, dioctyltin oxide, zinc 2-ethylhexanoate and zinc octylate; and
  • aqueous intermediate coating composition (A) various additives such as pigment dispersant, antifoaming agent, antioxidant, ultraviolet absorber, light stabilizer, surface regulator and gloss control agent may be appropriately blended, if desired.
  • the aqueous intermediate coating composition (A) may be prepared by mixing and dispersing the above-described components.
  • the solids content during coating is preferably adjusted to a range of preferably 45 mass % to 75 mass %, particularly preferably from 50 mass % to 70 mass %.
  • the aqueous intermediate coating composition (A) may be adjusted to a viscosity appropriate for the coating by adding an organic solvent and then applied and coated, if desired, by a conventional method such as rotary atomization coating, air spray or airless spray. From the viewpoint of smoothness, finish, etc. of the coated film, the coating composition may be applied to have a film thickness of usually 10 ⁇ m to 40 ⁇ m, preferably from 25 ⁇ m to 40 ⁇ m, based on the cured coated film.
  • the aqueous intermediate coated film obtained by applying the intermediate coating composition (A) can be cured per se, in the case of a baking drying, usually at a temperature of about 120° C. to about 180° C.
  • the cured intermediated coated film after heat-curing the coated film (intermediate coated film) formed by the aqueous intermediate coating composition (A) has an elongation at break at 20° C. of 20% to 30%, a Young's modulus of 5,000 kgf/cm 2 to 6,000 kgf/cm 2 , and a Tukon hardness of 4 to 6.
  • Young's modulus and Tukon hardness fall within the ranges above, both the chipping resistance and the adhesion to glass member can be satisfied.
  • the physical values above are physical values of a cured coated film cured under the heating conditions that the thickness of the intermediate coated film is 50 ⁇ m and the coated film is kept at 140° C. for 18 minutes.
  • the elongation at break and the Young's modulus are values obtained from applying the aqueous intermediate coating composition (A) onto a glass plate to have a film thickness of 50 ⁇ m based on the cured coated film, curing the coated film by heating under the conditions of keeping it at 140° C. for 18 minutes, then separating the coated film from the glass plate, cutting the coated film into a strip shape of 20 mm in length and 5 mm in width, and measuring the strip at a tensile speed of 4 mm/min in the longitudinal direction at 20° C. by means of “TENSILON UTM-II-20” (trade name, manufactured by Orientec Inc., TENSILON is a registered trademark).
  • the elongation at break is the ratio of an increment of length when the film is broken, to the original length before test.
  • the Young's modulus is the rising edge slope of a stress-strain curve.
  • the Tukon hardness is the value measured using TUKON (manufactured by American Chain & Cable Company, micro hardness tester) after a test coated plate prepared by applying the aqueous intermediate coating composition (A) onto an electrodeposited plate to have a film thickness of 30 ⁇ m based on the cured coated film and curing the coated film by heating under the conditions of keeping the coated film at 140° C. for 18 minutes is allowed to stand in a constant-temperature room at 20° C. for 4 hours.
  • Tukon hardness there is, for example, a method of adjusting the glass transition temperature (Tg) of the hydroxyl group-containing acrylic resin (a1).
  • Step (2) after preheating the intermediate coated film formed in step (1), an aqueous base coating composition (B) is applied to the intermediate coated film to form a base coated film.
  • the aqueous base coating composition (B) is a coating composition for imparting a design property to the multilayer coated film and enhancing the design property and depth feeling by lamination with the intermediate coated film.
  • the preheating temperature is preferably from 40 to 100° C., more preferably from 50 to 90° C., still more preferably from 60 to 80° C.
  • the preheating time is preferably from 30 seconds to 15 minutes, more preferably from 1 to 10 minutes, still more preferably from 2 to 5 minutes.
  • the solid content percentage of the intermediate coated film is preferably adjusted to fall within the range of usually from 70 to 100 mass %, preferably from 80 to 100 mass %, more preferably from 90 to 100 mass %, by performing the preheating above.
  • the base coated film is a coated film taking on a solid color causing no change in the hue depending on the observation angle.
  • the base coated film can be formed by applying an aqueous colored base coating composition.
  • the aqueous colored base coating composition usually contains a color pigment.
  • the color pigment include an organic pigment such as azo-based pigment, quinacridone-based pigment, diketopyrrolopyrrole-based pigment, perylene-based pigment, perinone-based pigment, benzimidazolone-based pigment, isoindoline-based pigment, isoindolinone-based pigment, azo metal chelate-based pigment, phthalocyanine-based pigment, indanthrone-based pigment, dioxazine-based pigment, threne-based pigment and indigo-based pigment; a metal oxide pigment such as titanium oxide pigment; and a carbon black pigment, and one of these pigments may be used alone, or two or more thereof may be used in combination.
  • the blending amount of the color pigment in the aqueous colored base coating composition is usually from 0.01 mass % to 150 mass %, preferably from 0.05 mass % to 120 mass %, relative to the total resin solids content in the aqueous colored base coating composition.
  • the color pigment to be blended in the aqueous colored base coating composition may be blended as a powder in the coating composition, but after the color pigment is mixed and dispersed with a part of the resin component to prepare a pigment dispersion in advance, the pigment dispersion may be mixed together with the remaining resin component or other components to form a coating composition.
  • conventional coating composition additives such as antifoaming agent, dispersant and surface regulator may be used, if desired.
  • the aqueous colored base coating composition may usually contain a resin component as a vehicle.
  • a resin component include those in which a base resin such as acrylic resin, polyester resin, alkyd resin and urethane resin, having a crosslinking functional group such as hydroxyl group, is used in combination with a crosslinking agent such as melamine resin, urea resin and polyisocyanate compound (including a blocked form), and these are used after being dissolved or dispersed in a solvent such as organic solvent and/or water.
  • a solvent such as water or organic solvent
  • various additives such as dispersant, antisettling agent, curing catalyst, antifoaming agent, antioxidant, ultraviolet absorber, surface regulator and rheology control agent, an extender pigment, etc. may be appropriately blended, if desired.
  • the aqueous colored base coating composition can be prepared by mixing and dispersing the above-described components.
  • the solids content during coating is preferably adjusted to a range of usually 12 mass % to 60 mass %, preferably from 15 mass % to 50 mass %, based on the coating composition.
  • the aqueous colored base coating composition may be adjusted to a viscosity appropriate for the coating by adding water, an organic solvent, etc. and then applied by electrostatic coating, air spray, airless spray or other methods and from the viewpoint of smoothness, the film thickness is usually from 5 ⁇ m to 30 ⁇ m, preferably from 5 ⁇ m to 25 ⁇ m, more preferably from 10 ⁇ m to 25 ⁇ m, based on the cured coated film.
  • the base coated film is a coated film taking on a metallic color causing a change in the hue depending on the observation angle.
  • the base coated film can be formed by applying an aqueous metallic base coating composition as the aqueous base coating composition (B).
  • the aqueous metallic base coating composition usually contains a flake-like effect pigment with the purpose of imparting a particle feeling to the coated film.
  • a flake-like effect pigment one kind or a combination of two or more kinds may be appropriately selected from light reflecting pigments and light interference pigments.
  • the light reflecting pigment examples include a flake-like metal pigment such as aluminum, copper, nickel alloy and stainless steel, a flake-like metal pigment in which the surface is coated with metal oxide, a flake-like metal pigment in which color pigment is chemically adsorbed or bonded to the surface, and a flake-like aluminum pigment in which an aluminum oxide layer is formed on the surface by inducing an oxidation reaction.
  • a flake-like aluminum pigment may be suitably used.
  • the flake-like aluminum pigment is usually produced by grinding and milling aluminum in the presence of a liquid grinding medium with use of a grinding aid in a ball mill or an attritor mill.
  • a grinding aid a higher fatty acid such as oleic acid, stearic acid, isostearic acid, lauric acid, palmitic acid and myristic acid, an aliphatic amine, an aliphatic amide, an aliphatic alcohol, etc.
  • an aliphatic hydrocarbon such as mineral spirit may be used.
  • the flake-like aluminum pigment can be roughly classified into a leafing type and a non-leafing type depending on the kind of the grinding aid.
  • a leafing type pigment When the leafing-type pigment is blended in the coating composition, flakes are arranged on the surface of the coated film (leafing) obtained by applying the coating composition, giving a finish with strong metallic feeling, and since the pigment has heat-reflecting action and exerts rust-preventing power, this type is often used for various building materials including a tank, a duct, pipings and roofing of production equipment, etc.
  • a flake-like aluminum pigment of a leafing type may be used, but in the case of using a flake-like aluminum pigment of this type, attention is required, because although it varies depending on the blending amount, the pigment may completely hide the surface by the effect of surface tension of the grinding aid in the process of forming the coated film and a particle feeling may not be expressed. From this viewpoint, a flake-like aluminum pigment of a non-leafing type is preferably used.
  • the particle diameter and thickness as used herein indicate the median diameter in a volume-basis particle size distribution measured by the laser diffraction scattering method by using a Microtrac particle size distribution measuring apparatus, MT3300 (trade name, manufactured by Nikkiso Co., Ltd.).
  • the average particle diameter is controlled to equal to or less than the upper limit above, the particle feeling of the coated film obtained can be avoided from becoming excessive, and this is advantageous in terms of design property, whereas if it is controlled to equal to or more than the lower limit, the particle feeling can be sufficient.
  • a light interference pigment may be used as the flake-like effect pigment.
  • a pigment obtained by coating a semitransparent substrate, such as natural mica, artificial mica, alumina flake, silica flake and glass flake, with a metal oxide may be used.
  • the metal oxide-coated mica pigment is a pigment in which the substrate is natural mica or artificial mica and the substrate surface is coated with a metal oxide.
  • the natural mica is a flake-like substrate obtained by grinding mica from ore, and the artificial mica is synthesized by heating an industrial raw material, such as SiO 2 , MgO, Al 2 O 3 , K 2 SiF 6 or Na 2 SiF 6 , melting the raw material at a high temperature of about 1,500° C., and cooling the melt for crystallization.
  • an industrial raw material such as SiO 2 , MgO, Al 2 O 3 , K 2 SiF 6 or Na 2 SiF 6 .
  • fluorine-based mica KMg 3 AlSi 3 O 10 F 2
  • potassium tetrasilicon mica KMg 25 AlSi 4 O 10 F 2
  • sodium tetrasilicon mica NaMg 25 AlSi 4 O 10 F 2
  • Na taeniolite NaMg 2 LiSi 4 O 10 F 2
  • LiNa taeniolite LiNaMg 2 LiSi 4 O 10 F 2
  • etc. are exemplified.
  • the metal oxide coat include titanium oxide and iron oxide. An interference color can be developed by the metal oxide coat.
  • the metal oxide-coated alumina flake pigment is a pigment in which the substrate is alumina flake and the substrate surface is coated with a metal oxide.
  • the alumina flake means a flake-like (foil-like) aluminum oxide and is colorless and transparent.
  • the alumina flake need not be an aluminum oxide single component and may contain an oxide of other metals. Examples of the metal oxide coat include titanium oxide and iron oxide. An interference color can be developed by the metal oxide coat.
  • the metal oxide-coated silica flake pigment is a pigment in which flake-like silica as a substrate having smooth surface and uniform thickness is coated with a metal oxide having a refractive index different from that of the substrate.
  • the metal oxide coat include titanium oxide and iron oxide. An interference color can be developed by the metal oxide coat.
  • the metal oxide-coated glass flake pigment is a pigment in which a flake-like glass substrate is coated with a metal oxide, and since the substrate surface is smooth, strong light reflection is caused to express a particle feeling.
  • the metal oxide coat include titanium oxide and iron oxide. An interference color can be developed by the metal oxide coat.
  • the light interference pigment may be subjected to a surface treatment so as to enhance the dispersibility, water resistance, chemical resistance, weather resistance, etc.
  • the size of the light interference pigment in the case of a light interference pigment using natural mica, artificial mica, alumina flake or silica flake as the substrate, from the viewpoint of finish appearance or particle feeling of the coated film, a pigment having an average particle diameter of usually 5 ⁇ m to 30 ⁇ m, preferably from 7 ⁇ m to 25 ⁇ m, may be suitably used.
  • a pigment having an average particle diameter of usually 15 ⁇ m to 100 ⁇ m, preferably from 17 ⁇ m to 45 ⁇ m, may be suitably used.
  • the particle diameter and thickness as used herein indicate the median diameter in a volume-basis particle size distribution measured by the laser diffraction scattering method by using a Microtrac particle size distribution measuring apparatus, MT3300 (trade name, manufactured by Nikkiso Co., Ltd.).
  • the average particle diameter is controlled to equal to or less than the upper limit above, the particle feeling of multilayer coated film, developed by the light interference pigment, can be prevented from becoming excessive, and this is advantageous in terms of design property, whereas if it is controlled to equal to or more than the lower limit, the particle feeling can be sufficient.
  • the content of the flake-like effect pigment in the aqueous metallic base coating composition is, in total, preferably from 0.01 mass % to 25 mass %, more preferably from 0.01 mass % to 15 mass %, further preferably from 0.05 mass % to 5 mass %, relative to the total solid content of the resin composition in the coating composition.
  • the aqueous metallic base coating composition may contain a color pigment with the purpose of adjusting the hue and brightness of the coated film obtained.
  • the color pigment include an inorganic pigment, e.g., a transparent iron oxide pigment, a composite oxide pigment such as titanium yellow, a titanium oxide pigment containing fine-particle titanium oxide, and a carbon black pigment; and an organic pigment such as azo-based pigment, quinacridone-based pigment, diketopyrrolopyrrole-based pigment, perylene-based pigment, perinone-based pigment, benzimidazolone-based pigment, isoindoline-based pigment, isoindolinone-based pigment, azo-metal chelate pigment, phthalocyanine-based pigment, indanthrone-based pigment, dioxazine-based pigment, threne-based pigment and indigo-based pigment.
  • an inorganic pigment e.g., a transparent iron oxide pigment, a composite oxide pigment such as titanium yellow, a titanium oxide pigment
  • the color pigment may be blended as a powder in the coating composition, or after the color pigment is mixed and dispersed with a part of the resin composition to prepare a pigment dispersion in advance, the pigment dispersion may be mixed together with the remaining resin component or other components to form a coating composition.
  • conventional coating composition additives such as antifoaming agent, dispersant and surface regulator may be used, if desired.
  • the blending amount thereof is usually from 0.01 mass % to 10 mass %, preferably from 0.01 mass % to 5 mass %, relative to the total solid content of the resin composition in the coating composition.
  • the aqueous metallic base coating composition usually contains a resin composition as a vehicle-forming component.
  • resin composition include those in which a base resin such as acrylic resin, polyester resin, alkyd resin and urethane resin, having a crosslinking functional group such as hydroxyl group, is used in combination with a crosslinking agent such as melamine resin, urea resin and polyisocyanate compound (including a blocked form), and these are used after being dissolved or dispersed in a solvent such as organic solvent and/or water.
  • a solvent such as water or organic solvent
  • various additives such as pigment dispersant, curing catalyst, antifoaming agent, antioxidant, ultraviolet absorber and surface regulator, a gloss control agent, an extender pigment, etc. may be appropriately blended, if desired.
  • the aqueous metallic base coating composition is prepared by mixing and dispersing the above-described components.
  • the solid content during coating is preferably adjusted to a range of usually 12 mass % to 60 mass %, preferably from 15 mass % to 50 mass %, based on the coating composition.
  • the aqueous metallic base coating composition may be adjusted to a viscosity appropriate for the coating by adding water or an organic solvent and then applied by a conventional method such as rotary atomization coating, air spray or airless spray.
  • the coating composition is preferably applied to have a film thickness of usually 10 ⁇ m to 25 ⁇ m based on the cured coated film and may be applied to have a film thickness of more preferably from 10 ⁇ m to 20 ⁇ m, still more preferably from 13 ⁇ m to 17 ⁇ m.
  • the aqueous coating composition is a term contrasted with an organic solvent-based coating composition and in general, means a coating composition obtained by dispersing and/or dissolving a coated film-forming resin, a pigment, etc. in water or a medium containing water as the main component (aqueous medium).
  • the base resin of the resin composition of the aqueous base coating composition (B) preferably has an acid group, and in the case of dispersion in water, from the viewpoint of enhancing water dispersibility, the acid group is preferably neutralized with a neutralizer so as to facilitate mixing and dispersion in water.
  • the neutralizer is not particularly limited as long as it can neutralize an acid group, and examples thereof include a basic compound such as sodium hydroxide, potassium hydroxide, trimethylamine, 2-(dimethylamino)ethanol, 2-amino-2-methyl-1-propanol, triethylamine and aqueous ammonia.
  • a basic compound such as sodium hydroxide, potassium hydroxide, trimethylamine, 2-(dimethylamino)ethanol, 2-amino-2-methyl-1-propanol, triethylamine and aqueous ammonia.
  • the base coated film obtained by applying the aqueous base coating composition (B) can be cured per se, in the case of a baking drying type, usually at a temperature of about 50° C. to about 180° C., and in the case of a normal temperature drying type or a forced drying type, can be cured usually at a temperature from room temperature to about 80° C.
  • Step (3) a base coated film obtained by applying the aqueous base coating composition (B) as above is preheated under heating conditions causing substantially no curing of the coated film, and a clear coating composition (C) is applied to the base coated film to form a clear coated film.
  • the preheating temperature is preferably from 40 to 100° C., more preferably from 50 to 90° C., still more preferably from 60 to 80° C.
  • the preheating time is preferably from 30 seconds to 15 minutes, more preferably from 1 to 10 minutes, still more preferably from 2 to 5 minutes.
  • the solid content percentage of the base coated film is suitably adjusted to fall within the range of usually from 70 to 100 mass %, preferably from 80 to 100 mass %, more preferably from 90 to 100 mass %, by performing the preheating above.
  • the clear coating composition (C) is a clear coating composition containing the hydroxyl group-containing acrylic resin (c1) and the allophanate group-containing polyisocyanate compound (c2).
  • the hydroxyl group-containing acrylic resin (c1) can be produced, for example, by (co)polymerizing at least one unsaturated monomer component having a hydroxyl group-containing unsaturated monomer and, depending on the case, further having other unsaturated monomers copolymerizable with the monomer above, under normal conditions.
  • the hydroxyl group-containing unsaturated monomer is a compound having at least one hydroxyl group and at least one polymerizable unsaturated bond per molecule, and examples thereof may include what is described in an explanation column of the hydroxyl group-containing acrylic resin (a1) above.
  • the hydroxyl value of the hydroxyl group-containing acrylic resin (c1) is preferably from 120 mg KOH/g to 200 mg KOH/g, more preferably from 130 mg KOH/g to 200 mg KOH/g, particularly more preferably from 140 mg KOH/g to 200 mg KOH/g from the viewpoint of satisfying both the scratch resistance and the water resistance.
  • the weight average molecular weight of the hydroxyl group-containing acrylic resin (c1) is preferably from 5,000 to 30,000, more preferably from 5,000 to 20,000, still more preferably from 8,000 to 20,000.
  • the weight average molecular weight is preferably from 5,000 to 30,000, more preferably from 5,000 to 20,000, still more preferably from 8,000 to 20,000.
  • the glass transition temperature of the hydroxyl group-containing acrylic resin (c1) is preferably from ⁇ 30° C. to 30° C., more preferably from ⁇ 20° C. to 20° C.
  • the glass transition temperature is ⁇ 30° C. or more, sufficient coating film hardness can be obtained, and when it is 30° C. or less, deterioration of the coated surface smoothness and crack resistance of the coating film can be prevented.
  • the hydroxyl group-containing acrylic resin (c1) also includes a so-called urethane-modified acrylic resin.
  • the hydroxyl group-containing acrylic resin (c1) may be used alone, or two or more thereof may be used in combination.
  • the coating composition includes a resin other than the hydroxyl group-containing acrylic resin (c1) as the base resin.
  • examples thereof include polyester resin, polyether resin, polyurethane resin and the like, and preferred examples thereof include hydroxyl group-containing polyester resin and a hydroxyl group-containing polyurethane resin.
  • the hydroxyl group-containing polyester resin (C) can be synthesized, for example, by an esterification reaction of a polybasic acid and a polyhydric alcohol in a usual manner.
  • the polybasic acid is a compound having two or more carboxyl groups per molecule and examples thereof include phthalic acid, isophthalic acid, terephthalic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, tetrahydrophthalic acid, hexahydrotrimellitic acid, maleic acid, fumaric acid, itaconic acid, trimellitic acid, pyromellitic acid, and anhydrides thereof.
  • the polyhydric alcohol is a compound having two or more hydroxyl groups per molecule and examples thereof include glycols such as ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2,2-dimethyl-1,3-propanediol, neopentyl glycol, 1,9-nonanediol, 1,4-cyclohexanediol, neopentyl glycol and hydroxypivalic acid-neopentyl glycol ester, 2-butyl-2-ethyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2,2,4-trimethylpentanediol, diols such as hydrogenated bisphenol A, and a trihydric or higher polyhydric polyol composition such as trimethylolpropane
  • An ⁇ -olefin epoxide such as propylene oxide or butylene oxide, a monoepoxy compound such as CARDURA E10 (produced by Japan Epoxy Resin Co., Ltd., trade name, a glycidyl ester of a synthetic hyperbranched saturated fatty acid), etc. is reacted with an acid, and the compound thereof may be introduced into the polyester resin.
  • the carboxyl group may be introduced, for example, by adding an acid anhydride to a hydroxyl group-containing polyester to cause half-esterification.
  • the hydroxyl value of the hydroxyl group-containing polyester resin is preferably from 100 mg KOH/g to 200 mg KOH/g, particularly preferably from 120 mg KOH/g to 180 mg KOH/g.
  • the weight average molecular weight of the hydroxyl group-containing polyester resin is preferably from 2,500 to 40,000, more preferably from 5,000 to 30,000.
  • hydroxyl group-containing polyurethane resin examples thereof include a hydroxyl group-containing polyurethane resin obtained by reacting a polyol and a polyisocyanate.
  • examples thereof as low-molecular-weight ones include divalent alcohol such as ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, and hexamethylene glycol; and trihydric alcohol such as trimethylolpropane, glycerin, and pentaerythritol.
  • examples thereof as high-molecular-weight ones include polyether polyol, polyester polyol, acrylic polyol, and epoxy polyol.
  • examples thereof include polyethylene glycol, polypropylene glycol, and polytetramethylene glycol.
  • polyester polyol examples thereof include alcohol such as the divalent alcohol, dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, and neopentyl glycol; polycondensate with dibasic acid such as adipic acid, azelaic acid, sebacic acid and the like; lactone type ring opening polymer polyol such as polycaprolactone; polycarbonate diol.
  • carboxyl group-containing polyols such as 2,2-dimethylolpropionic acid and 2,2-dimethylolbutanoic acid may also be used.
  • examples thereof include an aliphatic polyisocyanate compound such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, dimer acid diisocyanate, and lysine diisocyanate; and buret type adduct and isocyanurate ring adduct of polyisocyanate thereof; an alicyclic diisocyanate compound such as isophorone diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), methylcyclohexane-2,4- (or -2,6-) diisocyanate, 1,3- (or 1,4-) di (isocyanatomethyl) cyclohexane, 1,4-cyclohexane diisocyanate, 1,3-cyclopentane diisocyanate, and 1,2-cyclohexane diisocyanate; and buret type adduct and is
  • the hydroxyl value of the hydroxyl group-containing polyurethane resin is preferably from 80 mg KOH/g to 200 mg KOH/g, particularly preferably from 100 mg KOH/g to 180 mg KOH/g.
  • the weight average molecular weight of the hydroxyl group-containing polyurethane resin is preferably from 2,500 to 40,000, more preferably from 5,000 to 30,000.
  • the glass transition temperature of the hydroxyl group-containing polyurethane resin is preferably from ⁇ 40° C. to 85° C., more preferably from ⁇ 30° C. to 80° C.
  • the resin other than the hydroxyl group-containing acrylic resin (c1) is preferably 100 mass % or less, more preferably from 10 mass % to 50 mass %, relative to the total solid content of the hydroxyl group-containing acrylic resin (c 1).
  • the allophanate group-containing polyisocyanate compound (c2) is a compound obtained by subjecting a polyisocyanate selected from aliphatic polyisocyanate, alicyclic polyisocyanate, aromatic polyisocyanate and the like to an allophanatizing esterification reaction by a known method.
  • aliphatic polyisocyanate examples include a diisocyanate (C 2-16 alkane diisocyanate such as trimethylene diisocyanate, 1,2-propylene diisocyanate, tetramethylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, and 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate; and 2,6-diisocyanatomethylcaproate); and a polyisocyanate (such as lysine ester triisocyanate, and C 6-20 alkane triisocyanate such as 1,4,8-triisocyanatooctane, 1,6,11-triisocyanatoundecane, 1,8-diisocyanato-4-isocyanatomethyloctane, 1,3,6-
  • alicyclic polyisocyanate examples include a diisocyanate (such as 1,3-cyclopentene diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (common name: isophorone diisocyanate), 4,4′-methylenebis (cyclohexylisocyanate), methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 1,3- or 1,4-bis(isocyanatomethyl)cyclohexane (common name: hydrogenated xylylene diisocyanate) or a mixture thereof and norbornane diisocyanate); and a polyisocyanate (triisocyanate such as 1,3,5-triisocyanatocyclohexane, 1,3,5-trimethyl
  • aromatic polyisocyanate examples include a diisocyanate (such as 1,3- or 1,4-xylylene diisocyanate or a mixture thereof, ⁇ , ⁇ ′-diisocyanato-1,4-diethylbenzene, and 1,3- or 1,4-bis(1-isocyanato-1-methylethyl)benzene (common name: tetramethylxylylene diisocyanate) or a mixture thereof, m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, 2,4′- or 4,4′-diphenylmethane diisocyanate or a mixture thereof, 2,4- or 2,6-tolylene diisocyanate or a mixture thereof, 4,4′-toluidine diisocyanate and 4,4′-diphenylether diisocyanate); a polyis
  • the allophanate group-containing polyisocyanate compound (c2) of the aliphatic polyisocyanate is particularly preferable from the viewpoints of scratch resistance, hardness, yellowing resistance and the like of the coated film obtained.
  • hexamethylene diisocyanate is particularly preferable from the viewpoints of scratch resistance, hardness, yellowing resistance and the like of the coated film obtained.
  • the clear coating composition (C) may contain a polyisocyanate compound other than the allophanate group-containing polyisocyanate compound (c2), if desired.
  • Examples thereof include a biuret group-containing polyisocyanate compound obtained by biuretizing a polyisocyanate selected from an aliphatic polyisocyanate, an alicyclic polyisocyanate, an aromatic polyisocyanate, and the like by a known method; aliphatic polyisocyanates such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, dimer acid diisocyanate and lysine diisocyanate; isocyanurate ring adduct and uretdione type adducts of the aliphatic polyisocyanates thereof; alicyclic diisocyanates such as isophorone diisocyanate, 4,4′-methylenebis (cyclohexylisocyanate), and methylcyclohexane-2,4- or -2,6-diisocyanate; isocyanurate ring adduct of the alicyclic diisocyanates thereof; an aromatic di
  • the amount of the allophanate group-containing polyisocyanate compound (c2) used is that an equivalent ratio of NCO/OH, i.e. the isocyanate group (NCO) contained therein to the hydroxyl group (OH) in the clear coating composition (C) is preferably from 0.1 to 2.0, more preferably from 0.2 to 1.7, particularly more preferably from 0.6 to 1.5.
  • an equivalent ratio of NCO/OH, i.e. total isocyanate groups (NCO) contained in the allophanate group-containing polyisocyanate compound (c2) and polyisocyanate compound other than the allophanate group-containing polyisocyanate compound (c2) to the hydroxyl group (OH) in the clear coating composition (C), is preferably from 0.5 to 2.0, more preferably from 0.6 to 1.7, particularly more preferably from 0.7 to 1.5.
  • the clear coating composition (C) may contain, if desired, a color pigment, an effect pigment, a dye, etc. to an extent not impairing transparency and may further appropriately contain an extender pigment, a UV absorber, an antifoaming agent, a thickener, a rust-preventive agent, a surface conditioner, an organic solvent, etc.
  • the clear coating composition (C) can be applied to the coated film surface of the aqueous base coating composition (B) by a method known per se, such as airless spray, air spray and rotary atomizing coater, and static electricity may be applied during application of the coating composition.
  • the coated film thickness may be made to fall within the range of usually from 10 to 60 ⁇ m, preferably from 25 to 50 ⁇ m, in terms of cured film thickness.
  • the number average molecular weight and the weight average molecular weight are a value calculated from a chromatogram measured by gel permeation chromatography, based on the molecular weight of standard polystyrene.
  • the gel permeation chromatograph “HLC8120GPC” (manufactured by Tosoh Corporation) was used.
  • the measurement was performed using four columns of “TSKgel G-4000HXL”, “TSKgel G-3000HXL”, “TSKgel G-2500HXL” and “TSKgel G-2000HXL” (trade names, all manufactured by Tosoh Corporation) under the conditions of mobile phase: tetrahydrofuran, measurement temperature: 40° C., flow velocity: 1 cc/min, and detector: RI.
  • Step (4) the intermediate coated film, the base coated film and the clear coated film formed in the above steps (1) to (3), respectively, are heat-cured.
  • the clear coated film formed by applying the clear coating composition (C) is usually heat-cured simultaneously with the uncured base coated film.
  • the heating may be performed by a normal heating method of a coated film such as hot-air heating, infrared heating or high-frequency heating.
  • the heating temperature is preferably from 60° C. to 180° C., more preferably from 110° C. to 170° C., still more preferably from 130° C. to 160° C.
  • the heating time is not particularly limited but is preferably from 10 minutes to 90 minutes, more preferably from 15 minutes to 60 minutes, still more preferably from 15 minutes to 30 minutes.
  • preheating Before heat-curing, preheating may be appropriately performed.
  • the preheating temperature is preferably from 40° C. to 110° C., more preferably from 50° C. to 110° C.
  • the preheating time is preferably from 30 seconds to 15 minutes, more preferably from 1 minute to 10 minutes.
  • the multilayer coated film including an intermediate coated film, a base coated film and a clear coated film layer can be cured.
  • the film thickness is preferably from 70 ⁇ m to 120 ⁇ m, more preferably from 80 ⁇ m to 100 ⁇ m, based on the cured coated film.
  • step (5) in a part of an automotive body (for example, a portion to which front glass or rear glass is fixed), the following step (5) may be contained: an adhesive layer is formed on the clear coated film of the multilayer coated film including the intermediate coated film, the base coated film and the clear coated film, obtained according to the steps (1) to (4).
  • the embodiments of the step (5) are described below.
  • Step (5) in order to bond the automobile main body to a glass member, etc., an adhesive layer is formed on the clear coated film, usually in a frame shape corresponding to the shape of a glass member to be fixed.
  • a resin composition usually used as an adhesive, a sealing agent or a coating agent for example, urethane-based adhesives, acrylic adhesives, silicone-based adhesives, modified silicone-based adhesives, polysulfide-based adhesives, epoxy-based adhesives and PVC-based adhesives, may be used.
  • a urethane-based adhesive is preferably used.
  • the urethane-based adhesive may be sufficient if it is an adhesive having an isocyanate group, and the adhesive may be any of a thermosetting adhesive, a thermoplastic adhesive, etc.
  • urethane-based adhesive either one-pack type or two-pack type may be used, but in particular, a one-pack moisture-curable urethane-based adhesive is preferably used.
  • the adhesive examples include “3740”, “3765T” and “560F” (all trade names) produced by Sunstar Inc.; “WS373”, “WS282”, “WS202” and “WS252” (all trade names) produced by Yokohama Rubber Co., Ltd.; and “58702SFL” and “58702SFH” (both trade names) produced by Dow Chemical.
  • the method for applying the adhesive is not particularly limited, but from the viewpoint of productivity, in the automotive production line, coating by a robotic painting machine is widely performed in general.
  • the coating amount of the adhesive the adhesive is preferably applied to have a film thickness of usually approximately from 3 mm to 6 mm based on the cured coated film.
  • an adhesive layer is formed usually in a frame shape corresponding to the shape of a glass member to be fixed, on a part of an electrodeposition coated automotive body, a glass member such as front glass or rear window is laid thereon, and the adhesive layer is cured, whereby the glass member is fixed to the automotive body.
  • the hydroxyl group-containing acrylic resin (a1-1) obtained had a glass transition temperature of 5° C., a weight average molecular weight of 35,000, a hydroxyl value of 43 mgKOH/g, and an acid value of 47 mgKOH/g.
  • Solutions of hydroxyl group-containing acrylic resins (a1-2) to (a1-6) having a solid content concentration of 55% were obtained in the same manner as in the production of hydroxyl group-containing acrylic resin (a1-1) except that the blending formulation of the monomer mixture and the reaction temperature were changed as shown in Table 1.
  • the glass transition temperature, weight average molecular weight, hydroxyl value and acid value of each of the hydroxyl group-containing acrylic resins are shown together in Table 1.
  • Aqueous Intermediate Coating Composition (A1) 36 Parts (resin solid content: 20 parts) of the hydroxyl group-containing acrylic resin (a1-1) shown in Table 1, 90 parts of “JR-806” (trade name, produced by Tayca Corporation, rutile titanium dioxide), 0.1 parts of “Carbon MA-100” (trade name, produced by Mitsubishi Chemical Corporation, carbon black), and 5 parts of deionized water were mixed and after adjusting the pH to 8.0 with 2-(dimethylamino)ethanol, the mixture was dispersed by means of a paint shaker for 30 minutes to obtain a pigment dispersion paste.
  • JR-806 trade name, produced by Tayca Corporation, rutile titanium dioxide
  • Carbon MA-100 trade name, produced by Mitsubishi Chemical Corporation, carbon black
  • Aqueous intermediate coating compositions (A2) to (A16) having a viscosity of 45 seconds as measured with Ford cup No. 4 at 20° C. were obtained in the same manner as in the above production of aqueous intermediate coating composition (Al) except that respective raw materials were changed to raw materials each having the composition shown in Table 2 below.
  • the blending amount of each component is the amount (parts) of solid contents.
  • Polyester Resin (a3) Obtained by using trimethylolpropane, cyclohexanedimethanol, isophthalic acid and adipic acid and performing an esterification reaction in a usual manner; number average molecular weight of 4,500, hydroxyl value of 120, and acid value of 10.
  • Melamine Resin (a4) Imino group-containing methyl-butyl mixed etherified melamine; weight average molecular weight of 1,200.
  • Phosphate group-containing resin solution A mixed solvent of 27.5 parts of methoxypropanol and 27.5 parts of isobutanol was put in a reaction vessel equipped with a thermometer, a thermostat, a stirrer, a reflux condenser and a dropper and heated at 110° C., and then, 121.5 parts of a mixture containing 25 parts of styrene, 27.5 parts of n-butyl methacrylate, 20 parts of “Isostearyl Acrylate” (trade name, produced by Osaka Organic Chemical Industry, Ltd., branched higher alkyl acrylate), 7.5 parts of 4-hydroxybutyl acrylate, 15 parts of phosphate group-containing polymerizable monomer (note 2), 12.5 parts of 2-methacryloyloxyethyl acid phosphate, 10 parts of isobutanol and 4 parts of tert-butyl peroxyoctanoate was added to the mixed solvent above over 4 hours,
  • Phosphate group-containing polymerizable monomer 57.5 Parts of monobutylphosphoric acid and 41 parts of isobutanol were put in a reaction vessel equipped with a thermometer, a thermostat, a stirrer, a reflux condenser and a dropper, and after raising the temperature to 90° C., 42.5 parts of glycidyl methacrylate was added dropwise over 2 hours. The resulting mixture was further aged with stirring for 1 hour, and thereafter, 59 parts of isopropanol was added to obtain a phosphate group-containing polymerizable monomer solution having a solid content concentration of 50%. In the monomer obtained, the acid value by the phosphate group was 285 mgKOH/g.
  • Aqueous Base Coating Composition 100 Parts (solid content: 30 parts) of the hydroxyl group-containing acrylic acid aqueous dispersion (i), 73 parts (solid content: 40 parts) of the hydroxyl group-containing water-soluble acrylic resin (ii), 62 parts of the effect pigment concentrate (P-1), and 37.5 parts (solid content: 30 parts) of “CYMEL 325” (trade name, produced by ALLNEX LTD., melamine resin, solid content: 80%) were uniformly mixed, and “PRIMAL ASE-60” (trade name, produced by Rohm & Haas Co., thickener), 2-(dimethylamino)ethanol and deionized water were added thereto to obtain an aqueous base coating composition (B1) having a pH of 8.0, a solid content concentration of coating composition of 25%, and a viscosity of 40 seconds as measured with Ford cup No. 4 at 20° C.
  • the monomer emulsion (2) shown below was added dropwise over 1 hour and after aging for 1 hour, the mixture was cooled to 30° C. while gradually adding 40 parts of an aqueous 5% 2-(dimethylamino)ethanol solution to the reaction vessel, followed by filtering through a 100-mesh nylon cloth to obtain, as a filtrate, the hydroxyl group-containing acrylic resin aqueous dispersion (i) having an average particle diameter of 120 nm (as measured using a submicron particle size distribution analyzer “COULTER Model N4” (manufactured by Beckman Coulter, Inc.) at 20° C. after dilution with deionized water) and a solid content concentration of 30%.
  • the hydroxyl group-containing acrylic resin aqueous dispersion (i) had an acid value of 33 mgKOH/g and a hydroxyl value of 25 mgKOH/g.
  • Monomer Emulsion (1) 42 Parts of deionized water, 0.72 parts of “AQUALON KH-10”, 2.1 parts of methylenebisacrylamide, 2.8 parts of styrene, 16.1 parts of methyl methacrylate, 28 parts of ethyl acrylate, and 21 parts of n-butyl acrylate were mixed with stirring to obtain the monomer emulsion (1).
  • Monomer Emulsion (2) 18 Parts of deionized water, 0.31 parts of “AQUALON KH-10”, 0.03 parts of ammonium persulfate, 5.1 parts of methacrylic acid, 5.1 parts of 2-hydroxyethyl acrylate, 3 parts of styrene, 6 parts of methyl methacrylate, 1.8 parts of ethyl acrylate, and 9 parts of n-butyl acrylate were mixed with stirring to obtain the monomer emulsion (2).
  • the obtained hydroxyl group-containing acrylic resin (c1-1) solution was a homogeneous clear solution having a solid content of 60%.
  • the hydroxyl group-containing acrylic resin (c1-1) had a weight average molecular weight of about 10,000, a hydroxyl value of 151 mgKOH/g and a glass transition temperature of ⁇ 12° C.
  • Allophanate group-containing polyisocyanate compound (c2-1) Desmodur (trademark) N3580 produced by Covestro
  • An alloyed hot-dip galvanized steel plate subjected to zinc phosphate treatment was electrodeposition-coated with “ELECRON GT-10” (trade name, produced by Kansai Paint Co., Ltd., ELECRON being a registered trademark, thermosetting epoxy resin-based cationic electrodeposition coating composition) to have a thickness of 20 ⁇ m, followed by curing by heating at 170° C. for 30 minutes to prepare a test material to be coated.
  • “ELECRON GT-10” trade name, produced by Kansai Paint Co., Ltd., ELECRON being a registered trademark, thermosetting epoxy resin-based cationic electrodeposition coating composition
  • the aqueous intermediate coating composition (A1) obtained above was applied to the test material to be coated by a hand spray gun so as to provide a cured film thickness of 15 ⁇ m, followed by allowing to stand for 5 minutes, and then, the resultant product was preheated at 80° C. for 3 minutes.
  • the aqueous base coating composition (B1) obtained above was applied to the intermediate coated film by a hand spray gun so as to provide a cured film thickness of 10 ⁇ m, followed by allowing to stand for 5 minutes, and then, the resultant product was preheated at 80° C. for 3 minutes.
  • the clear coating composition (C1) obtained above was applied to the uncured base coated film by a hand spray gun so as to provide a cured film thickness of 25 ⁇ m, followed by allowing to stand for 7 minutes, and then, the resultant product was heated at 140° C. for 30 minutes, and the whole of the multilayer coated film was thus heat-cured to prepare a test plate.
  • the test plate was further coated with a urethane-based adhesive (trade name: “3740”, produced by Sunstar Inc., wind-shielding agent for automobiles) so as to provide a coated shape having a width of 20 mm, a thickness of 3 mm, and a length of 100 mm or more, and after putting a release paper thereon, they were uniformly pressed with a flat plate.
  • the flat plate was removed, and the test plate was then allowed to stand at a temperature of 23 ⁇ 2° C. and a humidity of 50 ⁇ 5% for 72 hours to cure the adhesive. After that, the release paper was peeled to prepare the test plate A for WDB (glass adhesion) test.
  • the aqueous intermediate coating composition (A1) obtained above was applied to the test material to be coated by a hand spray gun so as to provide a cured film thickness of 20 ⁇ m, followed by allowing to stand for 5 minutes, and the resultant product was preheated at 80° C. for 3 minutes.
  • the aqueous base coating composition (B1) obtained above was applied to the intermediate coated film by a hand spray gun so as to provide a cured film thickness of 15 ⁇ m, followed by allowing to stand for 5 minutes, and then, the resultant product was preheated at 80° C. for 3 minutes.
  • the clear coating composition (C1) obtained above was applied to the uncured base coated film by a hand spray gun so as to provide a cured film thickness of 35 ⁇ m, followed by allowing to stand for 7 minutes, and the resultant product was heated at 140° C. for 30 minutes, and the whole of the multilayer coated film was thus heat-cured to prepare the test plate B for chipping resistance test, scratch resistance test and coated film hardness test.
  • Each test plate (two kinds) was prepared in the same manner as in Example 1 except that the aqueous intermediate coating composition (A) was changed to the aqueous intermediate coating compositions (A2) to (A16), respectively, and the clear coating composition (C) was changed to the clear coating compositions (C2) to (C4), respectively.
  • the WDB adhesion (glass adhesion) test, chipping resistance test, scratch resistance test and coated film hardness test were performed based on the following test methods and evaluation methods.
  • the elongation at break, Young's modulus and Tukon hardness of the intermediate coated film were also measured by the above-described measurement methods. The test results are shown together in Table 2.
  • test plate A prepared above was immersed in a constant-temperature water bath set at 40° C. for 240 hours and then cooled by immersing it in water at 23° C. for 1 hour, and then, the following peel test was performed.
  • a cut reaching the coated film surface was formed at an angle of about 60° relative to the coated film by a cutter knife at intervals of 2 to 3 mm while manually pulling the cured adhesive layer in the direction at 90° or more relative to the coated film.
  • the peeled state after peeling the adhesive layer was evaluated in accordance with the following criteria “AA”, “A”, “B”, and “C”. In the following criteria, AA and A are regarded as being accepted.
  • A The coated film was not broken and only the adhesive layer was separated by cohesion failure, but adhesion between the coated film and the adhesive layer was substantially maintained.
  • the test plate B was placed on a sample holder of a flying stone chipping tester Model JA-400 (chipping test device) manufactured by Suga Test Instruments Co., Ltd., and 50 g of crushed granite stone with a particle size of No. 7 was hit against the test plate B at an angle of 45° by blowing compressed air at 0.392 MPa (4 kgf/cm 2 ) from a distance of 30 cm at ⁇ 20° C. Thereafter, the resulting test plate B was washed with water and dried, and a cloth pressure-sensitive adhesive tape (produced by Nichiban Co., Ltd.) was stuck to the coating surface. After peeling off the tape, scratch occurrence on the coated film were observed with an eye and the evaluation was made in accordance with the following criteria. In the following criteria, AA and A are regarded as being accepted.
  • AA The scratch size was extremely small, and the electrodeposition surface or raw steel plate was not exposed.
  • A The scratch size was small, and the electrodeposition surface or raw steel plate was not exposed.
  • the test plate B was stuck to an automobile with a water resistant tape produced by Nichiban Co., Ltd., and the automobile was washed with an automobile washing machine for 15 times under the condition of 20° C. After that, 20° mirror specular reflectance (20° gloss value) of the test plate B was measured and the gloss retention rate (%) with respect to the 20° gloss value before the test was measured, and the evaluation was made in accordance with the following criteria. The higher the gloss retention rate is, the better the scratch resistance is. As the automobile washing machine, “PO 20 FWRC” produced by Yasui Sangyo Co., Ltd. was used. In the following criteria, AA and A are regarded as being accepted.
  • the gloss retention rate is 85% or more
  • the gloss retention rate is 80% or more and less than 85%
  • the gloss retention rate is 70% or more and less than 80%
  • the gloss retention rate is 60% or more and less than 70%
  • the coated film hardness was measured using a TUKON hardness tester (TUKON microhardness tester, produced by American Chain & Cable Company) after leaving the test plate B in a constant-temperature chamber at 20° C. for 4 hours. The higher the value is, the harder the coated film is. In the following criteria, AA and A are regarded as being accepted.
  • the hardness is 10 or more
  • the hardness is 5 or more and less than 10

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Abstract

A method for forming a multilayer coated film includes step (1) of applying an aqueous intermediate coating composition (A), step (2) of applying an aqueous base coating composition (B), step (3) of applying a clear coating composition (C), and step (4) of heat-curing the coated films. The coating composition (A) contains a specific hydroxyl group-containing acrylic resin (a1), a specific polyurethane resin (a2), a specific hydroxyl group-containing polyester resin (a3), a melamine resin (a4), and an active methylene-blocked polyisocyanate compound (a5). A ratio of the resin (a1) to the resin (a2) falls within a specific range. The heat-cured coated film of the coating composition (A) has a specific elongation at break, Young's modulus and Tukon hardness. The coating composition (C) contains a hydroxyl group-containing acrylic resin (c1) and an allophanate group-containing polyisocyanate compound (c2).

Description

    CROSS-REFERENCE TO RELATED APPLICATIONS
  • This application claims priority from Japanese Patent Application No. 2018-090581 filed on May 9, 2018, the entire subject matter of which is incorporated herein by reference.
    • BACKGROUND OF THE INVENTION Technical Field
  • The present invention relates to a method for forming a multilayer coated film for coating an automotive body, the multilayer coated film being excellent in the chipping resistance, the scratching resistance, the coated film hardness and the adhesive strength when bonding to a member.
    • Background Art
  • On an object to be coated such as an automotive body, particularly an exterior panel part thereof, a multilayer coated film including an undercoat film excellent in the anticorrosive property, an intermediate coated film excellent in the smoothness and chipping resistance (chipping: damage to a coated film caused when hit by a small pebble, etc. flying from road), and a top coated film excellent in the appearance and the scratching resistance and the coated film hardness, as resistance to an environmental load, is usually formed on a steel plate for the purpose of imparting excellent anticorrosive property and appearance.
  • As a method of forming the multilayer coated film on the automobile body or the like as an object to be coated, from a viewpoint of shortening a coating time and reducing CO2 and VOC, the method of forming the multilayer coated film by the following aqueous 3 Wet system is used: after an aqueous intermediate coating composition is applied to perform intermediate coating, an aqueous color base coating composition is applied thereto to perform color base coating in a wet state as it is, and then, clear coating composition is also applied thereto to perform clear coating in the wet state, followed by burning them.
  • In conventional methods of forming a multilayer coated film by the aqueous 3 Wet system, the physical properties of the coated film are ensured by imparting functions to the intermediate coating composition and increasing the hardness of the coated film relatively. For example, Patent Document 1 discloses a method for forming a coated film using an intermediate coating composition containing (a) a urethane-modified polyester resin obtained by reacting an aliphatic diisocyanate compound with a hydroxyl group-containing polyester resin obtained by polycondensation of an acid component containing 80 mol % or more of isophthalic acid, and a polyhydric alcohol; (b) a melamine resin; (c) a hexamethylene diisocyanate compound blocked by an active methylene group-containing compound; (d) a nonaqueous dispersion resin having a core-shell structure; and (e) a flat pigment.
  • Patent Document 2 discloses a multilayer coated film on an external panel of an automotive body, etc., which is a multilayer coated film having formed therein, in the following order, an electrodeposition coated film, an intermediate coated film, a base coated film and a clear coated film, wherein at −20° C., the intermediate coated film has a Young's modulus of 35,000 kg/cm2 or more and an elongation at break of 2% or less and the clear coated film has a Young's modulus of 35,000 kg/cm2 or less and an elongation at break of 5% or more.
  • Furthermore, improvement of the scratching resistance is mainly achieved by imparting functions to the clear coat coating composition which forms the uppermost layer. For example, in the method of forming a multilayer coated film by two-coats and one-bake method in which the intermediate coated film is burned, the clear coating composition containing a hydroxyl group-containing acrylic resin and a polyisocyanate compound is used for the purpose of improving the scratching resistance.
  • As a clear coating composition containing the hydroxyl group-containing acrylic resin and the polyisocyanate compound, Patent Document 3 discloses a coating composition containing a hydroxyl group-containing resin (A) having a hydroxyl value of from 80 to 200 mgKOH/g and a weight average molecular weight of 2,500 to 40,000, a polyisocyanate compound (B), and a polycarbonate diol compound (C), as a diol component, having a viscosity at 50° C. of 10,000 mPa·s or less and a number average molecular weight of 400 to 2,500, obtained by reacting a diol having 2 to 10 carbon atoms with a carbonyl agent.
    • Patent Document 1: JP-A-2003-211085
    • Patent Document 2: JP-A-2006-239535
    • Patent Document 3: JP-A-2009-530425
    SUMMARY OF THE INVENTION
  • However, in the case of using an alloyed hot-dip galvanized steel plate as the steel plate above, the chipping resistance is sometimes reduced since the intermediate coated film has a rigidity, and further enhancement of the chipping resistance is needed. For example, in the method for forming a coated film described in Patent Document 1 and the multilayer coated film described in Patent Document 2, when an alloyed hot-dip galvanized steel plate is used as the steel plate, the chipping resistance may be insufficient due to the rigidity of the intermediate coated film.
  • In an automotive manufacturing specification, an adhesive layer is usually formed on the top coated film, and a member, for example, a glass member such as front glass or rear glass, is fixed onto the multilayer coated film through the adhesive layer, but when, for example, the intermediate coated film is softened with the intention to enhance the chipping resistance, the multilayer coated film below the adhesive layer may cause cohesion failure, or separation may occur between an electrodeposition coated film and the intermediate coated film, resulting in defective bonding to the member.
  • The clear coating composition containing the hydroxyl group-containing acrylic resin and the polyisocyanate compound is used in the usual method of forming a multilayer coated film by the aqueous 3 Wet system, the polyisocyanate compound permeates the base coated film and the intermediate coated film, and the physical properties thereof may be changed, resulting in decrease in scratch resistance and coated film hardness.
  • Accordingly, an object in an aspect of the present invention is to provide a method for forming a multilayer coated film, ensuring that in the method of forming a multilayer coated film by the aqueous 3 Wet system, even when an alloyed hot-dip galvanized steel plate is used as the steel plate, a multilayer coated film having more excellent chipping resistance than ever before and also having excellent adhesion strength for bonding to a member such as glass member, scratch resistance and coated film hardness can be formed.
  • As a result of intensive studies, the present inventors have found that in a method for forming a multilayer coated film, including sequentially applying an aqueous intermediate coating composition, an aqueous base coating composition, and a clear coating composition on/above an electrodeposition-coated alloyed hot-dip galvanized steel plate, thereby forming a multilayer coated film composed of an intermediate coated film, a base coated film and a clear coated film, when the aqueous intermediate coating composition use the coating composition which contains a hydroxyl group-containing acrylic resin (a1) having a glass transition temperature in a specific range and a weight average molecular weight in a specific range, a polyurethane resin (a2) having a glass transition temperature in a specific range, a hydroxyl group-containing polyester resin (a3), a melamine resin (a4), and an active methylene-blocked polyisocyanate compound (a5) and when the ratio of the hydroxyl group-containing acrylic resin (a1) to the polyurethane resin (a2) in the aqueous intermediate coating composition is controlled to a specific range and the elongation at break, Young's modulus and Tukon hardness of the coated film formed are controlled to specific ranges, and the clear coating composition use the coating composition which contains a hydroxyl group-containing acrylic resin (c1) and an allophanate group-containing polyisocyanate compound (c2), respectively, the above-described object can be attained. The present invention has been accomplished based on this finding.
  • That is, the present invention provides the following method.
  • A method for forming a multilayer coated film on an electrodeposition-coated alloyed hot-dip galvanized steel plate, the method comprising the following steps (1) to (4):
  • step (1): applying an aqueous intermediate coating composition (A) to an electrodeposition coated film, thereby forming an intermediate coated film on the electrodeposition coated film;
  • step (2): after preheating, applying an aqueous base coating composition (B) to the intermediate coated film, thereby forming a base coated film on the intermediate coated film;
  • step (3): after preheating, applying a clear coating composition (C) to the base coated film, thereby forming a clear coated film on the base coated film; and
  • step (4): heat-curing the intermediate coated film formed in the step (1), the base coated film formed in the step (2) and the clear coated film formed in the step (3),
  • wherein the aqueous intermediate coating composition (A) contains a hydroxyl group-containing acrylic resin (a1) having a glass transition temperature (Tg) of 5 to 15° C. and a weight average molecular weight of 30,000 to 40,000, a polyurethane resin (a2) having a glass transition temperature (Tg) of −50° C. or less and having a polyether skeleton, a hydroxyl group-containing polyester resin (a3), a melamine resin (a4), and an active methylene-blocked polyisocyanate compound (a5), a ratio of the hydroxyl group-containing acrylic resin (a1) to the polyurethane resin (a2) is from 20/10 to 30/10 in terms of solid content ratio, and the heat-cured coated film of the aqueous intermediate coating composition (A) has an elongation at break at 20° C. of 20 to 30%, a Young's modulus of 5,000 to 6,000 kgf/cm2, and a Tukon hardness of 4 to 6, and
  • wherein the clear coating composition (C) contains a hydroxyl group-containing acrylic resin (c1) and an allophanate group-containing polyisocyanate compound (c2).
  • According to the method for forming a multilayer coated film, the aqueous intermediate coating composition contains a hydroxyl group-containing acrylic resin (a1) having a glass transition temperature in a specific range and a weight average molecular weight in a specific range, a polyurethane resin (a2) having a glass transition temperature in a specific range, a hydroxyl group-containing polyester resin (a3), a melamine resin (a4), and an active methylene-blocked polyisocyanate compound (a5), the ratio of the hydroxyl group-containing acrylic resin (a1) to the polyurethane resin (a2) in the aqueous intermediate coating composition is controlled to a specific range, and the elongation at break, Young's modulus and Tukon hardness of the coated film formed are controlled to specific ranges, respectively, and the clear coating composition contains the hydroxyl group-containing acrylic resin (c1) and the allophanate group-containing polyisocyanate compound (c2) in the method of forming a multilayer coated film by the aqueous 3 Wet system. Thanks to such a configuration, even when an alloyed hot-dip galvanized steel plate is used as the steel plate, the multilayer coated film can have more excellent chipping resistance than ever before, and the adhesion strength for bonding of a member can be enhanced, and a coated film having excellent scratch resistance and coated film hardness can be formed.
  • Particularly, according to the method for forming a multilayer coated film, the multifunctional and high viscosity (high molecular weight) allophanate group-containing polyisocyanate compound is used in the clear coating composition, resulting in a possibility of controlling the permeation of the polyisocyanate compound to the base coated film and the intermediate coated film, and according to this, the excellent scratch resistance and coated film hardness can be realized.
    • DETAILED DESCRIPTION OF THE INVENTION
  • In the method for forming a multilayer coated film on an electrodeposition-coated alloyed hot-dip galvanized steel plate in an aspect of the present invention (hereinafter may be referred to as “the method of the present invention”), the method includes the following steps (1) to (4):
  • step (1): applying an aqueous intermediate coating composition (A) to an electrodeposition coated film, thereby forming an intermediate coated film on the electrodeposition coated film;
  • step (2): after preheating the intermediate coated film formed in the step (1), applying an aqueous base coating composition (B) to the intermediate coated film, thereby forming a base coated film on the intermediate coated film;
  • step (3): after preheating the base coated film formed in the step (2), applying a clear coating composition (C) to the base coated film, thereby forming a clear coated film on the base coated film; and
  • step (4): heat-curing the intermediate coated film formed in the step (1), the base coated film formed in the step (2) and the clear coated film formed in the step (3).
  • Subsequently to step (4), a step of forming an adhesive layer on the clear coated film may be provided as step (5).
  • The method for forming a multilayer coated film is described in detail below.
  • The material to be coated to which the method for forming a multilayer coated film is applied, is an electrodeposition-coated alloyed hot-dip galvanized steel plate and is usually used for an automotive body. A material of the automotive body may be appropriately subjected to a conventional surface treatment.
  • The electrodeposition coating composition that may be used for electrodeposition coating may be either a cationic resin-based composition or an anionic resin-based composition and may be either a water-soluble composition or a water-dispersible composition, and a coating composition known per se may be used. In coating an automobile, from the viewpoint of anticorrosive properties or the like, a cationic resin-based composition is usually used, and a cationic electrodeposition coating composition containing a cationic resin may be suitably used.
  • Specific examples of the cationic electrodeposition coating composition include a cationic electrodeposition coating composition containing a cationic base resin having a cationic group and a crosslinking functional group such as hydroxyl group, carboxyl group and amino group (e.g., an epoxy resin, an acrylic resin, a polybutadiene resin, each modified with an amino group-containing compound), and a crosslinking agent such as blocked polyisocyanate compound, epoxy resin and melamine resin.
  • In the cationic electrodeposition coating composition, it is preferred that a neutralizer for the base resin, a color pigment, an anticorrosive pigment, an extender pigment, a hydrophilic organic solvent, etc. are usually further blended, if desired.
  • The electrodeposition coating composition can be applied by an ordinary method depending on an electrodeposition coating composition to be used. In the case of applying a cationic electrodeposition coating composition, specifically, electrodeposition coating may be performed in a usual manner, for example, by diluting the coating composition with deionized water to a solids mass concentration of preferably about 5 mass % to about 40 mass % and keeping the pH usually at 5.5 to 8.0. The coated film may be heat-cured at a temperature of usually about 140° C. to about 210° C., preferably at a temperature of 150° C. to 180° C., for usually 10 minutes to 60 minutes, preferably for 20 minutes to 30 minutes. The thickness of the coated film is preferably from about 10 μm to about 60 μm, particularly preferably from 15 μm to 30 μm, based on the cured coated film.
    • <Step (1)>
  • According to the method, first, in the step (1), an aqueous intermediate coating composition (A) is applied onto an electrodeposition coated film of an electrodeposition-coated alloyed hot-dip galvanized steel plate to form an intermediate coated film. In general, the intermediate coating composition is applied for the purpose of forming an intermediate coated film layer between an undercoat film and a top coated film to contribute to enhancement of adhesion among layers of the multilayer coated film and covering the roughness on a surface of a material to be coated to improve finish appearance, chipping resistance, etc.
    • <<Aqueous Intermediate Coating Composition (A)>>
  • In the method, the aqueous intermediate coating composition (A) contains a hydroxyl group-containing acrylic resin (a1), a polyurethane resin (a2), a hydroxyl group-containing polyester resin (a3), a melamine resin (a4), and an active methylene-blocked polyisocyanate compound (a5), and additionally contains, if desired, a pigment (F) and an organic solvent (G).
  • <<Hydroxyl Group-Containing Acrylic Resin (a1)>>
  • The hydroxyl group-containing acrylic resin (a1) can be produced, for example, by (co)polymerizing at least one unsaturated monomer component having a hydroxyl group-containing unsaturated monomer and, depending on the case, further having other unsaturated monomer(s) copolymerizable with the monomer above, under normal conditions.
  • The hydroxyl group-containing unsaturated monomer is a compound having at least one hydroxyl group and at least one polymerizable unsaturated bond per molecule, and examples thereof include a monoesterified product of a (meth)acrylic acid with a dihydric alcohol having a carbon number of 2 to 8, such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate and 4-hydroxybutyl (meth)acrylate; an ε-caprolactone-modified monoesterified product of a (meth)acrylic acid and a dihydric alcohol having a carbon number of 2 to 8; an allyl alcohol; and a (meth)acrylate having a polyoxyethylene chain having a hydroxyl group at a molecular terminal.
  • In the present specification, (meth)acrylate is a generic term of acrylate and methacrylate, and (meth)acrylic acid is a generic term of acrylic acid and methacrylic acid.
  • Examples of the other unsaturated monomer(s) copolymerizable with the above-described hydroxyl group-containing unsaturated monomer include an alkyl (meth)acrylate or cycloalkyl (meth)acrylate, such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, i-propyl (meth)acrylate, n-butyl (meth)acrylate, i-butyl (meth)acrylate, tert-butyl (meth)acrylate, n-hexyl(meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, tridecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, “Isostearyl Acrylate” (trade name, produced by Osaka Organic Chemical Industry, Ltd.), cyclohexyl (meth)acrylate, methylcyclohexyl (meth)acrylate, tert-butylcyclohexyl (meth)acrylate, cyclododecyl (meth)acrylate; an isobornyl group-containing unsaturated monomer such as isobornyl (meth)acrylate; an adamantyl group-containing unsaturated monomer such as adamantyl (meth)acrylate; an aromatic ring-containing unsaturated monomer such as styrene, α-methylstyrene, vinyltoluene and phenyl (meth)acrylate; an alkoxysilyl group-containing unsaturated monomer such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, γ-(meth)acryloyloxypropyltrimethoxysilane and γ-(meth)acryloyloxypropyltriethoxysilane; a perfluoroalkyl (meth)acrylate such as perfluorobutylethyl (meth)acrylate and perfluorooctylethyl (meth)acrylate; an unsaturated monomer having fluorinated alkyl group such as fluoroolefin; an unsaturated monomer having a photopolymerizable functional group such as maleimide group; a vinyl compound such as N-vinylpyrrolidone, ethylene, butadiene, chloroprene, vinyl propionate and vinyl acetate; a carboxy group-containing unsaturated monomer such as (meth)acrylic acid, maleic acid, crotonic acid and β-carboxyethyl acrylate; a nitrogen-containing unsaturated monomer such as (meth)acrylonitrile, (meth)acrylamide, dimethylaminopropyl (meth)acrylamide, dimethylaminoethyl (meth)acrylate, and an adduct of glycidyl (meth)acrylate with amines; an epoxy group-containing unsaturated monomer such as glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, 3,4-epoxycyclohexylethyl (meth)acrylate, 3,4-epoxycyclohexylpropyl (meth)acrylate and allyl glycidyl ether; a (meth)acrylate having a polyoxyethylene chain having an alkoxy group at a molecular terminal; a sulfonic acid group-containing unsaturated monomer such as 2-acrylamido-2-methylpropanesulfonic acid, allylsulfonic acid, sodium styrenesulfonate, sulfoethyl methacrylate and its sodium salt or ammonium salt; a phosphoric acid group-containing unsaturated monomer such as 2-acryloyloxyethyl acid phosphate, 2-methacryloyloxyethyl acid phosphate, 2-acryloyloxypropyl acid phosphate and 2-methacryloyloxypropyl acid phosphate; an UV-absorbing group-containing unsaturated monomer such as 2-hydroxy-4-(3-methacryloyloxy-2-hydroxypropoxy)benzophenone, 2-hydroxy-4-(3-acryloyloxy-2-hydroxypropoxy)benzophenone, 2,2′-dihydroxy-4-(3-methacryloyloxy-2-hydroxypropoxy)benzophenone, 2,2′-dihydroxy-4-(3-acryloyloxy-2-hydroxypropoxy)benzophenone and 2-(2′-hydroxy-5′-methacryloyloxyethylphenyl)-2H-benzotriazole; an unsaturated monomer having UV stabilizing performance, such as 4-(meth)acryloyloxy-1,2,2,6,6-pentamethylpiperidine, 4-(meth)acryloyloxy-2,2,6,6-tetramethylpiperidine, 4-cyano-4-(meth)acryloylamino-2,2,6,6-tetramethylpiperidine, 1-(meth)acryloyl-4-(meth)acryloylamino-2,2,6,6-tetramethylpiperidine, 1-(meth)acryloyl-4-cyano-4-(meth)acryloylamino-2,2,6,6-tetramethylpiperidine, 4-crotonoyloxy-2,2,6,6-tetramethylpiperidine, 4-crotonoylamino-2,2,6,6-tetramethylpiperidine and 1-crotonoyl-4-crotonoyloxy-2,2,6,6-tetramethylpiperidine; and a carbonyl group-containing unsaturated monomer such as acrolein, diacetone acrylamide, diacetone methacrylamide, acetoacetoxyethyl methacrylate, formylstyrol and vinyl alkyl ketone having 4 to 7 carbon atoms (e.g., vinyl methyl ketone, vinyl ethyl ketone, and vinyl butyl ketone). One of these may be used alone, or two or more thereof may be used in combination.
  • The hydroxyl group-containing acrylic resin (a1) has a glass transition temperature (Tg) of from 5 to 15° C. When Tg falls within the range above, the chipping resistance can be enhanced.
  • In the present specification, the glass transition temperature Tg of the hydroxy group-containing acrylic resin is a value calculated in accordance with the following formula:

  • 1/Tg(K)=W1/T1+W2/T2+ . . . Wn/Tn

  • Tg(° C.)=Tg(K)−273
  • wherein W1, W2, . . . Wn are mass fractions of respective monomers, and T1, T2 . . . . Tn are glass transition temperatures Tg (K) of homopolymers of respective monomers.
  • The glass transition temperature of a homopolymer of each monomer is a value from POLYMER HANDBOOK, Fourth Edition, compiled by J. Brandrup, E. H. Immergut, and E. A. Grulke (1999), and as for the glass transition temperature of a monomer not described in the document, a value obtained by synthesizing a homopolymer of the monomer to have a weight average molecular weight of about 50,000 and measuring the glass transition temperature thereof by differential scanning thermal analysis is used.
  • The hydroxyl group-containing acrylic resin (a1) has a weight average molecular weight of from 30,000 to 40,000. When the weight average molecular weight falls within the range above, the chipping resistance can be enhanced.
  • Furthermore, from the viewpoint of storage stability or water resistance of the coated film obtained, the hydroxyl group-containing acrylic resin (a1) may have a hydroxyl value of usually from 1 to 200 mgKOH/g, preferably from 2 to 100 mgKOH/g, more preferably from 3 to 60 mgKOH/g, and an acid value of usually from 1 to 200 mgKOH/g, preferably from 2 to 150 mgKOH/g, more preferably from 5 to 100 mgKOH/g.
  • In the present specification, the hydroxyl value (mgKOH/g) of the resin is expressed by the number of mg of potassium hydroxide equivalent to the hydroxyl content of 1 g of the resin. A molecular weight of potassium hydroxide is 56.1.
  • In the present specification, the acid value (mgKOH/g) of the resin is expressed by the number of mg of potassium hydroxide equivalent to the acid content of 1 g of the resin. The molecular weight of potassium hydroxide is 56.1.
  • <<Polyurethane Resin (a2)>>
  • The polyurethane resin (a2) has a glass transition temperature (Tg) of −50° C. or less and has a polyether skeleton. Preferable examples of the polyurethane resin (a2) include the following urethane resin emulsion (a2-i).
  • Examples of the urethane resin emulsion (a2-i) include a urethane resin emulsion produced from a polyisocyanate component (a2-i-1) and a polyol component (a2-i-2) in accordance with a conventional method.
  • Examples of the polyisocyanate component (a2-i-1) include diisocyanate and other polyisocyanates.
  • The diisocyanate as a raw material of the urethane resin emulsion (a2-i) is not particularly limited, and one kind of or a mixture of two or more kinds of diisocyanates widely used in this technical field may be used. Examples of the diisocyanate include an aromatic diisocyanate such as tolylene diisocyanate, diphenylmethane-4,4′-diisocyanate, p-phenylene diisocyanate, xylylene diisocyanate, 1,5-naphthylene diisocyanate, 3,3′-dimethyldiphenyl-4,4′-diisocyanate, dianisidine diisocyanate and tetramethylxylylene diisocyanate; an alicyclic diisocyanate such as isophorone diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, trans-1,4-cyclohexyl diisocyanate and norbornene diisocyanate; and an aliphatic diisocyanate such as 1,6-hexamethylene diisocyanate, 2,2,4- and/or (2,4,4)-trimethylhexamethylene diisocyanate and lysine diisocyanate.
  • In a preferred embodiment, the diisocyanate above may be used in the form of a blocked isocyanate blocked with various blocking agents. The content (mass %) of diisocyanate in the polyisocyanate component (a2-i-1) is preferably from 10 to 60%, more preferably from 20 to 40%, from the viewpoint of chipping resistance.
  • Another polyisocyanate as a raw material of the urethane resin emulsion (a2-i) is a polyisocyanate having three or more isocyanate group per molecule. Examples thereof include isocyanurate trimer, biuret trimer, and trimethylolpropane adduct of the above-exemplified diisocyanates; and a trifunctional or higher functional isocyanate such as triphenylmethane triisocyanate, 1-methylbenzole-2,4,6-triisocyanate and dimethyltriphenylmethane tetraisocyanate, and such an isocyanate compound may be used in the form of a product modified by carbodiimide, isocyanurate, biuret, etc. or may be used in the form of a blocked isocyanate blocked with various blocking agents.
  • Examples of the polyol component (a2-i-2) include a polyol having a polyether skeleton that imparts a polyether skeleton to the polyurethane resin (a2). Examples of such a polyol include a polyoxyalkylene glycol such as polyethylene glycol, polypropylene glycol, poly(ethylene)propylene glycol and polytetramethylene glycol; and an ethylene oxide and/or propylene oxide adduct of a polyhydric alcohol. Examples of the polyhydric alcohol include aliphatic diols such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,4-butanediol, neopentyl glycol, 3-methyl-2,4-pentanediol, 2,4-pentanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 2-methyl-2,4-pentanediol, 2,4-diethyl-1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 3,5-heptanediol, 1,8-octanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, diethylene glycol and triethylene glycol; alicyclic diols such as cyclohexanedimethanol and cyclohexanediol; and a trihydric or higher polyhydric alcohol such as trimethylolethane, trimethylolpropane, hexitols, pentitols, glycerin, pentaerythritol and tetramethylolpropane. When the polyurethane resin (a2) has a polyether skeleton, excellent chipping resistance can be exhibited.
  • The ratio of the polyisocyanate component (a2-i-1) to the polyol component (a2-i-2) is not particularly limited, but in a preferred embodiment, the polyol component (a2-i-2) is used in a ratio of preferably from 40 to 90 mass %, more preferably from 50 to 80 mass %, relative to total mass of the polyisocyanate component (a2-i-1) and the polyol component (a2-i-2) used for the production of the urethane resin emulsion (a2-i).
  • In addition to the polyisocyanate component (a2-i-1) and the polyol component (a2-i-2), an amine component (a2-i-3) may be used as a raw material in order to, e.g., form a urea bond or achieve a high molecular weight. Examples of the amine component (a2-i-3) include a monoamine compound and a diamine compound.
  • The monoamine compound is not particularly limited, and one kind of or a mixture of two or more kinds of monoamine compounds widely used in this technical filed may be used. Examples of the monoamine compound include an alkylamine such as ethylamine, propylamine, 2-propylamine, butylamine, 2-butylamine, tertiary-butylamine and isobutylamine; an aromatic amine such as aniline, methylaniline, phenylnaphthylamine and naphthylamine; an alicyclic amine such as cyclohexaneamine and methylcyclohexaneamine; an ether amine such as 2-methoxyethylamine, 3-methoxypropylamine and 2-(2-methoxyethoxy)ethylamine; and an alkanolamine such as ethanolamine, propanolamine, butylethanolamine, 1-amino-2-methyl-2-propanol, 2-amino-2-methylpropanol, diethanolamine, diisopropanolamine, dimethylaminopropylethanolamine, dipropanolamine, N-methylethanolamine and N-ethylethanolamine. Among these, an alkanolamine imparts good water dispersion stability to a polyurethane molecule and is preferred, and 2-aminoethanol and diethanolamine are more preferred because of low cost.
  • The diamine compound is not particularly limited, and one kind of or a mixture of two or more kinds of diamine compounds widely used in this technical field may be used. Examples of the diamine compound include low molecular diamines obtained by substituting an alcoholic hydroxyl group of the above-exemplified low molecular diols with an amino group, such as ethylenediamine and propylenediamine; polyether diamines such as polyoxypropylene diamine and polyoxyethylene diamine; alicyclic diamines such as menthenediamine, isophoronediamine, norbornenediamine, bis(4-amino-3-methyldicyclohexyl)methane, diaminodicyclohexylmethane, bis(aminomethyl)cyclohexane and 3,9-bis(3-aminopropyl)2,4,8,10-tetraoxaspiro(5,5)undecane; aromatic diamines such as m-xylenediamine, α-(m/p aminophenyl)ethylamine, m-phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, diaminodiethyldimethyldiphenylmethane, diaminodiethyldiphenylmethane, dimethylthiotoluenediamine, diethyltoluenediamine and α,α′-bis(4-aminophenyl)-p-diisopropylbenzene; hydrazine; and a dicarboxylic acid dihydrazide compound that is a compound between a dicarboxylic acid exemplified by a polyvalent carboxylic acid used for the above-described polyester polyol, and hydrazine. Among these diamine compounds, the low molecular weight diamines are preferred because of low cost, and ethylenediamine is more preferred.
  • In the urethane resin emulsion (a2-i), an internal branching agent and an internal crosslinking agent capable of providing a branch and a crosslinked structure to a polyurethane molecule may be used, in addition to the components (a2-i-1) to (a2-i-3). As the internal branching agent and internal crosslinking agent, examples thereof include trimethylolpropane.
  • The method of producing the urethane resin emulsion (a2-i) is not particularly limited, and a method widely used in this technical field may be used. Preferable examples of the production method include a method of synthesizing a prepolymer or a polymer in a solvent that is inert to the reaction and has high affinity for water, and feeding and dispersing it into water. Examples thereof include (i) a method of synthesizing a prepolymer from the polyisocyanate component (a2-i-1) and the polyol component (a2-i-2) in the solvent above, and reacting it in water with the amine component (a2-i-3) that is used, if desired; and (ii) a method of synthesizing a polymer from the polyisocyanate component (a2-i-1), the polyol component (a2-i-2), and the amine component (a2-i-3) that is used, if desired, and feeding and dispersing it into water. In addition, a neutralizer component may be previously added to water into which the prepolymer or polymer is fed, or may be added after feeding.
  • As the solvent being inert to the reaction and having high affinity for water, which is used in the above-described suitable production method, examples thereof include acetone, methyl ethyl ketone, dioxane, tetrahydrofuran, and N-methyl-2-pyrrolidone. Such a solvent is usually used in a ratio of 3 to 100 mass % relative to the total amount of those raw materials used for the production of prepolymer.
  • In the above production method, the blending ratio is not particularly limited. The blending ratio may be replaced by the molar ratio in a reaction stage between an isocyanate group in the polyisocyanate component (a2-i-1) and an isocyanate reactive group in the polyol component (a2-i-2) and the amine component (a2-i-3) that is used, if desired. As for the molar ratio, if an unreacted isocyanate group is lack in dispersed polyurethane molecules, adhesiveness of the coated film and/or strength of the coated film may be reduced when the polyurethane resin is used for a coating composition, and if an unreacted isocyanate group is present in an excessive amount, it may affect dispersion stability and/or physical properties of the coating composition. For this reason, the molar ratio of an isocyanate reactive group is preferably from 0.5 to 2.0 when assuming an isocyanate group is 1. Furthermore, the molar ratio of an isocyanate reactive group in the polyol component (a2-i-2) is preferably from 0.3 to 1.0, more preferably from 0.5 to 0.9, when assuming an isocyanate group in the polyisocyanate component (a2-i-1) is 1. The molar ratio of an isocyanate reactive group in the amine component (a2-i-3) that is used, if desired, is preferably from 0.1 to 1.0, more preferably from 0.2 to 0.5, when assuming an isocyanate group in the polyisocyanate component is 1.
  • In order to stabilize the dispersibility of the urethane resin emulsion (a2-i), one kind of or two or more kinds of emulsifiers such as surfactant may be used. The particle diameter thereof is not particularly limited but is preferably 1 μm or less, more preferably 500 nm or less, because good dispersion state can be maintained.
  • As the emulsifier, an anionic surfactant, a nonionic surfactant, a cationic surfactant, an amphoteric surfactant, a high molecular surfactant, a reactive surfactant, etc., which are widely used in this technical field and used in a urethane resin emulsion, may be used. In the case of using the emulsifier, for the reason that the cost is low and good emulsification is obtained, an anionic surfactant, a nonionic surfactant and a cationic surfactant are preferred.
  • Examples of the anionic surfactant include alkyl sulfates such as sodium dodecyl sulfate, potassium dodecyl sulfate and ammonium dodecyl sulfate; sodium dodecyl polyglycol ether sulfate; sodium sulforicinoleate; an alkyl sulfonate such as alkali metal salt of sulfonated paraffin and ammonium salt of sulfonated paraffin; a fatty acid salt such as sodium laurate, triethanolamine oleate and triethanolamine abietate; an alkylaryl sulfonate such as sodium benzene sulfonate and alkali metal sulfate of alkali phenol hydroxyethylene; a higher alkylnaphthalenesulfonate; a naphthalenesulfonic acid-formalin condensate; a dialkylsulfosuccinate; a polyoxyethylene alkyl sulfate; and a polyoxyethylene alkylaryl sulfate.
  • Examples of the nonionic surfactant include an ethylene oxide and/or propylene oxide adduct of an alcohol having a carbon number of 1 to 18, an ethylene oxide and/or propylene oxide adduct of an alkylphenol, and an ethylene oxide and/or propylene oxide adduct of an alkylene glycol and/or an alkylene diamine.
  • As the alcohol having a carbon number of 1 to 18 constituting the nonionic surfactant, examples thereof include methanol, ethanol, propanol, 2-propanol, butanol, 2-butanol, tertiary-butanol, amyl alcohol, isoamyl alcohol, tertiary-amyl alcohol, hexanol, octanol, decane alcohol, lauryl alcohol, myristyl alcohol, palmityl alcohol, and stearyl alcohol. Examples of the alkylphenols include phenol, methylphenol, 2,4-di-tertiary-butylphenol, 2,5-di-tertiary-butylphenol, 3,5-di-tertiary-butylphenol, 4-(1,3-tetramethylbutyl)phenol, 4-isooctylphenol, 4-nonylphenol, 4-tertiary-octylphenol, 4-dodecylphenol, 2-(3,5-dimethylheptyl)phenol, 4-(3,5-dimethylheptyl)phenol, naphthol, bisphenol A, and bisphenol F. Examples of the alkylene glycol include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, and 1,6-hexanediol. Examples of the alkylene diamine include these alkylene glycols in which an alcoholic hydroxy group is substituted with an amino group. The ethylene oxide and propylene oxide adducts may be a random adduct or a block adduct.
  • Examples of the cationic surfactant include primary to tertiary amine salts, a pyridinium salt, an alkyl pyridinium salt, and a quaternary ammonium salt such as alkyl halide quaternary ammonium salt.
  • In the case of using such an emulsifier, the amount thereof is not particularly limited, and the emulsifier may be used in any amount, but when the amount used is 0.01 or more in terms of mass ratio when assuming the urethane resin is 1, sufficient dispersibility is obtained, and when the molar ratio is 0.3 or less when assuming the urethane resin is 1, reduction in the physical properties such as water resistance, strength and elongation of the coated film, etc. obtained from an aqueous first colored coating composition can be prevented.
  • As the urethane resin emulsion (a2-i), a commercial product may be used. Examples of the commercial product include “Bayhydrol” series produced by Covestro; “Superflex” (registered trademark) series produced by Dai-Ichi Kogyo Seiyaku Co., Ltd.); and “PERMARIN” (registered trademark) series and “UCOAT” (registered trademark) series produced by Sanyo Chemical Industries, Ltd.
  • In the urethane resin emulsion (a2-i), the solid content thereof is not particularly limited, and any value may be selected. The solid content is preferably from 10 to 50 mass % because of good dispersibility and coating performance, and more preferably from 20 to 40 mass %.
  • The average molecular weight of the urethane resin dispersed in the urethane resin emulsion (a2-i) is not particularly limited, and any range, in which dispersibility as an aqueous coating composition is imparted and a good coated film is formed, may be selected. The weight average molecular weight is preferably from 1,000 to 500,000, more preferably from 5,000 to 200,000. The hydroxyl value is also not particularly limited, and any value may be selected. The acid value is expressed in consumption (mg) of KOH per gram of resin and is usually from 0 to 100 mgKOH/g.
  • The glass transition temperature (Tg) of the urethane resin dispersed in the urethane resin emulsion (a2-i) is −50° C. or less. When Tg falls within this range, the chipping resistance can be enhanced. Tg is preferably from −80 to −50° C., more preferably from −75 to −50° C.
  • In the present specification, the glass transition temperature (Tg) of the urethane resin above is a value measured using a dynamic viscoelasticity measuring apparatus and can be a value in the catalogue of the raw material manufacturer.
  • <<Hydroxyl Group-Containing Polyester Resin (a3)>>
  • The hydroxyl group-containing polyester resin (a3) can be synthesized by a known method of subjecting a polybasic acid and a polyhydric alcohol to an esterification reaction in a usual manner. The hydroxyl group-containing polyester resin (a3) preferably has an acid group such as carboxyl group.
  • The polybasic acid is a compound having two or more carboxyl groups per molecule and examples thereof include phthalic acid, isophthalic acid, terephthalic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, naphthalenedicarboxylic acid, 4,4-diphenyldicarboxylic acid, diphenylmethane-4,4′-dicarboxylic acid, HET acid, maleic acid, fumaric acid, itaconic acid, trimellitic acid, pyromellitic acid, cyclohexane-1,3-dicarboxylic acid, cyclohexane-1,4-dicarboxylic acid, hexahydrophthalic acid, hexahydroisophthalic acid, hexahydroterephthalic acid, tetrahydrophthalic acid, hexahydrotrimellitic acid, methylhexahydrophthalic acid, and anhydrides thereof.
  • The polyhydric alcohol is a compound having two or more hydroxyl groups per molecule and examples thereof include glycols such as ethylene glycol, propylene glycol, diethylene glycol, trimethylene glycol, tetraethylene glycol, triethylene glycol, dipropylene glycol, 1,4-butanediol, 1,3-butanediol, 2,3-butanediol, 1,2-butanediol, 3-methyl-1,2-butanediol, 1,2-pentanediol, 1,5-pentanediol, 1,4-pentanediol, 2,4-pentanediol, 2,3-dimethyltrimethylene glycol, tetramethylene glycol, 3-methyl-4,5-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 1,6-hexanediol, 1,5-hexanediol, 1,4-hexanediol, 2,5-hexanediol, neopentyl glycol and hydroxypivalic acid-neopentyl glycol ester; a polylactonediol formed by adding lactones such as ε-caprolactone to the glycols above; polyester diols such as bis(hydroxyethyl)terephthalate; 1,3-cyclohexanedimethanol; 1,4-cyclohexanedimethanol; tricyclodecanedimethanol; hydrogenated bisphenol A; hydrogenated bisphenol F; spiroglycol; dihydroxymethyltricyclodecane; glycerin; trimethylolpropane; trimethylolethane; diglycerin; triglycerin; 1,2,6-hexanetriol; pentaerythritol; dipentaerythritol; dipentaerythritol; sorbitol; mannitol; and a hydroxycarboxylic acid such as 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, 2,2-dimethylolpentanoic acid, 2,2-dimethylolhexanoic acid and 2,2-dimethyloloctanoic acid.
  • As the hydroxyl group-containing polyester resin (a3), a fatty acid-modified polyester resin modified with, e.g., a (semi)drying oil fatty acid such as linseed oil fatty acid, coconut oil fatty acid, safflower oil fatty acid, soybean oil fatty acid, sesame oil fatty acid, perilla oil fatty acid, hempseed oil fatty acid, tall oil fatty acid and dehydrated castor oil fatty acid, may also be used. In general, the modification amount with such a fatty acid is suitably 30 mass % or less in terms of oil length. In addition, the hydroxyl group-containing polyester resin (a3) may be a resin in which a part of a monobasic acid such as benzoic acid is reacted.
  • The hydroxyl group-containing polyester resin (a3) may also be a resin in which an α-olefin epoxide such as propylene oxide or butylene oxide, a monoepoxy compound such as CARDURA E10 (produced by Momentive Specialty Chemicals Inc., trade name, a glycidyl ester of a synthetic hyperbranched saturated fatty acid), etc. is reacted with an acid group in the polyester resin.
  • In the case of introducing a carboxyl group into the polyester resin, the carboxyl group may be introduced, for example, by adding an acid anhydride to a hydroxyl group-containing polyester resin to cause half-esterification.
  • The hydroxyl value of the hydroxyl group-containing polyester resin (a3) is preferably from 10 mg KOH/g to 250 mg KOH/g, particularly preferably from 40 mg KOH/g to 170 mg KOH/g, from the viewpoint of finish appearance and curability of the coated film.
  • In a case where the hydroxyl group-containing polyester resin (a3) has an acid group, the acid value is preferably from 1 mg KOH/g to 100 mg KOH/g, particularly preferably from 5 mg KOH/g to 60 mg KOH/g, from the viewpoint of curability and adhesion of the coated film.
  • The number average molecular weight of the hydroxyl group-containing polyester resin (a3) is preferably from 1,000 to 50,000, particularly preferably from 1,000 to 10,000, from the viewpoint of curability and finish appearance of the coated film. Here, the number average molecular weight of the hydroxyl group-containing polyester resin (a3) is determined by gel permeation chromatograph (GPC).
  • <<Melamine Resin (a4)>>
  • A melamine resin (a4) is contained as an aqueous crosslinking agent component of the intermediate coating composition (A).
  • As the melamine resin, examples thereof include a partially methylolated melamine resin or a fully methylolated melamine resin, obtained by the reaction of a melamine component and an aldehyde component. Examples of the aldehyde component include formaldehyde, paraformaldehyde, acetaldehyde, benzaldehyde, etc.
  • In addition, a methylolated melamine resin in which the methylol group is etherified in part or in whole with an appropriate alcohol may also be used. Examples of the alcohol to be used for the etherification include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, 2-ethyl-1-butanol, and 2-ethyl-1-hexanol.
  • The melamine resin is preferably a methyl-etherified melamine resin obtained by etherifying, in part or in whole, the methylol group of a partially or fully methylolated melamine resin with methyl alcohol, a butyl-etherified melamine resin obtained by etherifying, in part or in whole, the methylol group of a partially or fully methylolated melamine resin with butyl alcohol, or a methyl-butyl mixture-etherified melamine resin obtained by etherifying, in part or in whole, the methylol group of a partially or fully methylolated melamine resin with methyl alcohol and butyl alcohol, more preferably a methyl-butyl mixture-etherified melamine resin.
  • The weight average molecular weight of the melamine resin is preferably from 400 to 6,000, more preferably from 500 to 4,000, still more preferably from 600 to 3,000.
  • A commercially available melamine resin can be used as the melamine resin. As the trade name of the commercially available melamine resin, examples thereof include “CYMEL 202”, “CYMEL 203”, “CYMEL 204”, “CYMEL 211”, “CYMEL 212”, “CYMEL 238”, “CYMEL 251”, “CYMEL 253”, “CYMEL 254”, “CYMEL 303”, “CYMEL 323”, “CYMEL 324”, “CYMEL 325”, “CYMEL 327”, “CYMEL 350”, “CYMEL 370”, “CYMEL 380”, “CYMEL 385”, “CYMEL 1156”, “CYMEL 1158”, “CYMEL 1116”, and “CYMEL 1130” (trade names, all produced by Allnex Japan Inc., CYMEL is a registered trademark); “RESIMENE 735”, “RESIMENE 740”, “RESIMENE 741”, “RESIMENE 745”, “RESIMENE 746”, and “RESIMENE 747” (trade names, all produced by Monsanto Co., Ltd.); “U-VAN 120”, “U-VAN 20HS”, “U-VAN 205E”, “U-VAN 2021”, “U-VAN 2028”, and “U-VAN 28-60” (trade names, all produced by Mitsui Chemicals, Inc., U-VAN is a registered trademark); and “SUMIMAL M55”, “SUMIMAL M30W”, and “SUMIMAL M50W” (trade names, all produced by Sumitomo Chemical Co., Ltd., SUMIMAL is a registered trademark).
  • <<Active Methylene-Blocked Polyisocyanate Compound (a5)>>
  • Examples of the active methylene-blocked polyisocyanate compound (a5) include a blocked polyisocyanate compound obtained by reacting an active methylene compound with an isocyanate group in a polyisocyanate compound. An active methylene-blocked polyisocyanate compound (a5-i) having a hydrophilic group is particularly preferred.
  • As the compound (a5-i), a blocked polyisocyanate compound (a5-i-3) obtained by reacting an active hydrogen-containing compound having a hydrophilic group with a part of isocyanate groups in a polyisocyanate compound (a5-i-1) to introduce the hydrophilic group, and further reacting an active methylene compound (a5-i-2) with an isocyanate group in the polyisocyanate compound (a5-i-1) may be preferably used. Furthermore, a compound obtained by reacting a secondary alcohol (a5-i-4) having a carbon number of 6 or more with the blocked polyisocyanate compound (a5-i-3) may be preferably used.
  • The polyisocyanate compound (a5-i-1) has at least two isocyanate groups per molecule and examples thereof include an aliphatic polyisocyanate, an alicyclic polyisocyanate, an aromatic-aliphatic polyisocyanate, an aromatic polyisocyanate, and derivatives of these polyisocyanates.
  • Examples of the aliphatic polyisocyanate include an aliphatic diisocyanate such as trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, dimer acid diisocyanate and methyl 2,6-diisocyanatohexanoate (common name: lysine diisocyanate); and an aliphatic triisocyanate such as 2-isocyanatoethyl 2,6-diisocyanatohexanoate, 1,6-diisocyanato-3-isocyanatomethylhexane, 1,4,8-triisocyanatooctane, 1,6,11-triisocyanatoundecane, 1,8-diisocyanato-4-isocyanatomethyloctane, 1,3,6-triisocyanatohexane and 2,5,7-trimethyl-1,8-diisocyanato-5-isocyanatomethyloctane.
  • Examples of the alicyclic polyisocyanate include an alicyclic diisocyanate such as 1,3-cyclopentene diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (common name: isophorone diisocyanate), 4-methyl-1,3-cyclohexylene diisocyanate (common name: hydrogenated TDI), 2-methyl-1,3-cyclohexylene diisocyanate, 1,3- or 1,4-bis(isocyanatomethyl)cyclohexane (common name: hydrogenated xylylene diisocyanate) or a mixture thereof, methylenebis(4,1-cyclohexanediyl) diisocyanate (common name: hydrogenated MDI) and norbornane diisocyanate; and an alicyclic triisocyanate such as 1,3,5-triisocyanatocyclohexane, 1,3,5-trimethylisocyanatocyclohexane, 2-(3-isocynatopropyl)-2,5-di(isocyanatomethyl)-bicyclo(2.2.1)heptane, 2-(3-isocyanatopropyl)-2,6-di(isocyanatomethyl)-bicyclo(2.2.1)heptane, 3-(3-isocyanatopropyl)-2,5-di(isocyanatomethyl)-bicyclo(2.2.1)heptane, 5-(2-isocyanatoethyl)-2-isocyanatomethyl-3-(3-isocyanatopropyl)-bicyclo(2.2.1)heptane, 6-(2-isocyanatoethyl)-2-isocyanatomethyl-3-(3-isocyanatopropyl)-bicyclo(2.2.1)heptane, 5-(2-isocyanatoethyl)-2-isocyanatomethyl-2-(3-isocyanatopropyl)-bicyclo(2.2.1)-heptane and 6-(2-isocyanatoethyl)-2-isocyanatomethyl-2-(3-isocyanatopropyl)-bicyclo(2.2.1)heptane.
  • Examples of the aromatic-aliphatic polyisocyanate include an aromatic-aliphatic diisocyanate such as methylenebis(4,1-phenylene)diisocyanate (common name: MDI), 1,3- or 1,4-xylylene diisocyanate or a mixture thereof, ω,ω′-diisocyanato-1,4-diethylbenzene, and 1,3- or 1,4-bis(1-isocyanato-1-methylethyl)benzene (common name: tetramethylxylylene diisocyanate) or a mixture thereof; and an aromatic-aliphatic triisocyanate such as 1,3,5-triisocyanatomethylbenzene.
  • Examples of the aromatic polyisocyanate include an aromatic diisocyanate such as m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4′-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 2,4-tolylene diisocyanate (common name: 2,4-TDI) or 2,6-tolylene diisocyanate (common name: 2,6-TDI) or a mixture thereof, 4,4′-toluidine diisocyanate and 4,4′-diphenylether diisocyanate; an aromatic triisocyanate such as triphenylmethane-4,4′,4″-triisocyanate, 1,3,5-triisocyanatobenzene and 2,4,6-triisocyanatotoluene; and an aromatic tetraisocyanate such as 4,4′-diphenylmethane-2,2′,5,5′-tetraisocyanate.
  • Examples of the derivative of the polyisocyanate include a dimer, a trimer, a biuret, an allophanate, a urethodione, a urethoimine, an isocyanurate, an oxadiazinetrione, a polymethylene polyphenyl polyisocyanate (crude MDI; polymeric MDI), and a crude TDI, of the above-described polyisocyanate.
  • One of the above-described polyisocyanates and derivatives thereof may be used alone, or two or more thereof may be used in combination. Among these polyisocyanates, an aliphatic diisocyanate, an alicyclic diisocyanate, and a derivative thereof are preferred as the polyisocyanate compound (a5-i-1), because yellowing is less likely to occur during heating of the obtained blocked polyisocyanate compound (a5-i-1). Above all, from the viewpoint of improving flexibility of the formed coated film, an aliphatic diisocyanate and a derivative thereof are more preferred.
  • As the active hydrogen-containing compound having a hydrophilic group, examples thereof include an active hydrogen-containing compound having a nonionic hydrophilic group, an active hydrogen-containing compound having an anionic hydrophilic group, and an active hydrogen-containing compound having a cationic hydrophilic group, and one of these may be used alone, or two or more thereof may be used in combination. Among these, an active hydrogen-containing compound having a nonionic hydrophilic group is preferably used, because the reaction of blocking an isocyanate group in the polyisocyanate compound (a5-i-1) by the active methylene compound (a5-i-2) is less likely to be inhibited.
  • As the active hydrogen-containing compound having a nonionic hydrophilic group, for example, an active hydrogen-containing compound having a polyoxyalkylene group is preferred. Examples of the polyoxyalkylene group include a polyoxyethylene group and a polyoxypropylene group, and one of these may be used alone, or two or more thereof may be used in combination. Among these, from the viewpoint of storage stability of the coating composition, an active hydrogen-containing compound having a polyoxyethylene group is preferred.
  • From the viewpoint of, e.g., storage stability of the coating composition and adhesion of the formed multilayer coated film, the active hydrogen-containing compound having a polyoxyethylene group preferably contains 3 or more continuous oxyethylene groups, more preferably from 5 to 100 continuous oxyethylene groups, still more preferably from 8 to 45 continuous oxyethylene groups.
  • The active hydrogen-containing compound having a polyoxyethylene group may contain an oxyalkylene group except for an oxyethylene group, in addition to the continuous oxyethylene groups. As the oxyalkylene group except for the oxyethylene group, examples thereof include an oxypropylene group, an oxybutylene group, and an oxystyrene group. In the active hydrogen-containing compound having a polyoxyethylene group, from the viewpoint of storage stability of the coating composition, the molar ratio of the oxyethylene group in the oxyalkylene group is preferably from 20 to 100 mol %, more preferably from 50 to 100 mol %. When the molar ratio of the oxyethylene group in the oxyalkylene group is 20 mol % or more, sufficient hydrophilicity can be imparted and therefore, reduction in the storage stability of the coating composition can be prevented.
  • In the active hydrogen-containing compound having a nonionic hydrophilic group, from the viewpoint of storage stability of the coating composition and water resistance of the formed multilayer coated film, the number average molecular weight is preferably from 200 to 2,000. From the viewpoint of storage stability of the coating composition, the lower limit of the number average molecular weight is preferably 300, more preferably 400. From the viewpoint of water resistance of the formed multilayer coated film, the upper limit is preferably 1,500, more preferably 1,200.
  • As the active hydrogen-containing compound having a nonionic hydrophilic group, examples thereof include a polyethylene glycol monoalkyl ether (another name: ω-alkoxy polyoxyethylene) such as polyethylene glycol monomethyl ether and polyethylene glycol monoethyl ether; a polypropylene glycol monoalkyl ether (another name: ω-alkoxy polyoxypropylene) such as polypropylene glycol monomethyl ether and polypropylene glycol monoethyl ether; an ω-alkoxy polyoxyethylene (oxypropylene) such as ω-methoxy polyoxyethylene (oxypropylene) and ω-ethoxy polyoxyethylene (oxypropylene); a polyethylene glycol (propylene glycol) monoalkyl ether such as polyethylene glycol (propylene glycol) monomethyl ether and polyethylene glycol (propylene glycol) monoethyl ether; and polyethylene glycol, polypropylene glycol, polyethylene glycol (propylene glycol), α-(aminoalkyl)-ω-alkoxypolyoxyethylene, α-(aminoalkyl)-ω-alkoxypolyoxypropylene, and α-(aminoalkyl)-ω-alkoxypolyoxyethylene (oxypropylene), and one of these may be used alone, or two or more thereof may be used in combination. Among these, polyethylene glycol monomethyl ether, polyethylene glycol monoethyl ether, and polyethylene glycol are preferred, and polyethylene glycol monomethyl ether is more preferred.
  • As the commercial product of the polyethylene glycol monomethyl ether, examples thereof include “Uniox M-400”, “Uniox M-550”, “Uniox M-1000”, and “Uniox M-2000” (trade names, all produced by NOF Corporation, Uniox is a registered trademark). Examples of the commercial product of the polyethylene glycol include “PEG #200”, “PEG #300”, “PEG #400”, “PEG #600”, “PEG #1000”, “PEG #1500”, “PEG #1540”, and “PEG #2000” (trade names, all produced by NOF Corporation).
  • The reaction of a part of isocyanate groups in the polyisocyanate compound (a5-i-1) with the active hydrogen-containing compound having a hydrophilic group can be performed at 0 to 150° C., and a solvent may be used. In this case, the solvent is preferably an aprotic solvent and is particularly preferably an ester, an ether, an N-alkylamide, a ketone, etc. The active hydrogen-containing compound which has not reacted with an isocyanate group in the polyisocyanate compound (a5-i-1) can be removed after the completion of reaction. As for the reaction ratio of the polyisocyanate compound (a5-i-1) and the active hydrogen-containing compound having a hydrophilic group, from the viewpoint of storage stability and curability of the coating composition and smoothness, clearness and adhesion of the formed multilayer coated film, the number of moles of the active hydrogen in the active hydrogen-containing compound is preferably from 0.03 to 0.6 mol, more preferably from 0.04 to 0.4 mol, per mol of the isocyanate group in the polyisocyanate compound (a5-i-1).
  • Examples of the active methylene compound (a5-i-2) include a malonic acid diester such as dimethyl malonate, diethyl malonate, di-n-propyl malonate, diisopropyl malonate, di-n-butyl malonate, diisobutyl malonate, di-sec-butyl malonate, di-tert-butyl malonate, di-n-pentyl malonate, di-n-hexyl malonate, di(2-ethylhexyl) malonate, methyl isopropyl malonate, ethyl isopropyl malonate, methyl n-butyl malonate, ethyl n-butyl malonate, methyl isobutyl malonate, ethyl isobutyl malonate, methyl sec-butyl malonate, ethyl sec-butyl malonate, diphenyl malonate and dibenzyl malonate; an acetoacetic acid ester such as methyl acetoacetate, ethyl acetoacetate, n-propyl acetoacetate, isopropyl acetoacetate, n-butyl acetoacetate, isobutyl acetoacetate, sec-butyl acetoacetate, tert-butyl acetoacetate, n-pentyl acetoacetate, n-hexyl acetoacetate, 2-ethylhexyl acetoacetate, phenyl acetoacetate and benzyl acetoacetate; and an isobutyrylacetic acid ester such as methyl isobutyrylacetate, ethyl isobutyrylacetate, n-propyl isobutyrylacetate, isopropyl isobutyrylacetate, n-butyl isobutyrylacetate, isobutyl isobutyrylacetate, sec-butyl isobutyrylacetate, tert-butyl isobutyrylacetate, n-pentyl isobutyrylacetate, n-hexyl isobutyrylacetate, 2-ethylhexyl isobutyrylacetate, phenyl isobutyrylacetate and benzyl isobutyrylacetate. One of these may be used alone, or two or more thereof may be used in combination.
  • From the viewpoint of smoothness and clearness of the formed multilayer coated film, the active methylene compound (a5-i-2) is preferably at least one compound selected from the group consisting of dimethyl malonate, diethyl malonate, diisopropyl malonate, methyl acetoacetate, ethyl acetoacetate, methyl isobutyrylacetate and ethyl isobutyrylacetate, and more preferably at least one compound selected from the group consisting of diisopropyl malonate, methyl isobutyrylacetate and ethyl isobutyrylacetate. Among these, from the viewpoint of smoothness and clearness of the formed multilayer coated film as well as reactivity of the obtained blocked polyisocyanate compound (a5-i-1) and storage stability of the coating composition, the compound is still more preferably diisopropyl malonate.
  • In the reaction of blocking an isocyanate group by the active methylene compound (a5-i-2), a reaction catalyst may be used, if desired. Examples of the reaction catalyst include a basic compound such as metal hydroxide, metal alkoxide, metal carboxylate, metal acetylacetonate, hydroxide of an onium salt, onium carboxylate, metal salt of an active methylene compound, onium salt of an active methylene compound, aminosilanes, amines and phosphines. As the onium salt, an ammonium salt, a phosphonium salt, and a sulfonium salt are preferred. The amount of the reaction catalyst used is preferably from 10 to 10,000 ppm, more preferably from 20 to 5,000 ppm, based on the total solid mass of the polyisocyanate compound (a5-i-1) and the active methylene compound (a5-i-2).
  • The reaction of blocking an isocyanate group by the active methylene compound (a5-i-2) can be performed at 0 to 150° C., and a solvent may be used. In this case, the solvent is preferably an aprotic solvent, more preferably an ester, an ether, an N-alkylamide, a ketone, etc. When the reaction proceeds as intended, the reaction may be terminated by adding an acid component to neutralize the basic compound as a catalyst.
  • In the reaction of blocking an isocyanate group by the active methylene compound (a5-i-2), the amount of the active methylene compound (a5-i-2) used is not particularly limited, but is preferably from 0.1 to 3 mol, more preferably from 0.2 to 2 mol, per mol of the isocyanate group in the polyisocyanate compound (a5-i-1). The active methylene compound which has not been reacted with an isocyanate group in the polyisocyanate compound (a5-i-1) can be removed after the completion of blocking reaction.
  • Other than the active methylene compound (a5-i-2), a blocking agent such as alcohol-based blocking agents, phenol-based blocking agents, oxime-based blocking agents, amine-based blocking agents, acid amide-based blocking agents, imidazole-based blocking agents, pyridine-based blocking agents and mercaptan-based blocking agents may be used in combination.
  • As described above, an isocyanate group in the polyisocyanate compound (a5-i-1) is reacted with the active methylene compound (a5-i-2) to obtain a blocked polyisocyanate compound (a5-i-3). The blocked polyisocyanate compound (a5-i-3) may be further reacted with a secondary alcohol (a5-i-4) having a carbon number of 6 or more.
  • As the secondary alcohol (a5-i-4) having a carbon number of 6 or more, examples thereof include 4-methyl-2-pentanol, 5-methyl-2-hexanol, 6-methyl-2-heptanol, and 7-methyl-2-octanol. One of these may be used alone, or two or more thereof may be used in combination.
  • The reaction of the blocked polyisocyanate compound (a5-i-3) and the secondary alcohol (a5-i-4) is preferably performed by a method of removing a part or all of the alcohol derived from active methylene in the blocked polyisocyanate compound (a5-i-3) by distillation from the system under heating, reduced pressure, etc., and promoting the reaction.
  • As the production method above, specifically, it is suitable to remove a part or all of the alcohol at a temperature of usually from 20 to 150° C., preferably from 75 to 95° C., over 5 minutes to 20 hours, preferably over 10 minutes to 10 hours, by reducing the pressure, if desired.
  • As for the blending ratio of the blocked polyisocyanate compound (a5-i-3) and the secondary alcohol (a5-i-4), the ratio of the secondary alcohol (a5-i-4) is preferably from 5 to 500 parts by mass, more preferably from 10 to 200 parts by mass, based on 100 parts by mass of the solid content of the blocked polyisocyanate compound (a5-i-3).
  • In the reaction of the blocked polyisocyanate compound (a5-i-3) and the secondary alcohol (a5-i-4), in order to control the molecular weight of the blocked polyisocyanate compound (a5-i-1), the above-described removing operation may be performed after adding a polyfunctional hydroxy group-containing compound to the blocked polyisocyanate compound (a5-i-3) and the secondary alcohol (a5-i-4).
  • From the viewpoint of compatibility with other components of the coating composition and smoothness, clearness, water resistance, chipping resistance, etc. of the formed multilayer coated film, the number average molecular weight of the blocked polyisocyanate compound (a5-i-1) obtained as above is preferably from 600 to 30,000, more preferably from 900 to 10,000.
  • In the aqueous intermediate coating composition (A), the ratio of the hydroxyl group-containing acrylic resin (a1) to the polyurethane resin (a2) (i.e. (former/latter)) is from 20/10 to 30/10 in terms of solid content ratio. If the ratio of the hydroxyl group-containing acrylic resin (a1) is less than the lower limit above, the chipping resistance and the adhesion to a glass member may deteriorate, whereas if it exceeds the upper limit above, the chipping resistance may deteriorate.
  • In the aqueous intermediate coating composition (A), from the viewpoint of enhancing the chipping resistance and the adhesion strength for bonding of a member, the ratio of the components (a1), (a2), (a3), (a4) and (a5) (solid contents) is preferably in the following ranges based on 100 parts by mass of the resin solid content in the aqueous intermediate coating composition (A):
  • hydroxyl group-containing acrylic resin (a1): usually from 5 to 30 parts by mass, preferably from 10 to 30 parts by mass, more preferably from 20 to 30 parts by mass;
  • polyurethane resin (a2): usually from 5 to 20 parts by mass, preferably from 5 to 15 parts by mass, more preferably from 8 to 12 parts by mass;
  • hydroxyl group-containing polyester resin (a3): usually from 10 to 40 parts by mass, preferably from 15 to 35 parts by mass, more preferably from 20 to 30 parts by mass;
  • melamine resin (a4): usually from 10 to 40 parts by mass, preferably from 15 to 35 parts by mass, more preferably from 20 to 30 parts by mass;
  • active methylene-blocked polyisocyanate compound (a5): usually from 5 to 25 parts by mass, preferably from 5 to 15 parts by mass, more preferably from 8 to 12 parts by mass.
    • <<Pigment (F)>>
  • As the pigment (F), a pigment usually employed for a coating composition may be used. Specifically, a color pigment such as titanium dioxide, zinc white, carbon black, phthalocyanine blue, Prussian blue, cobalt blue, azo pigment, phthalocyanine pigment, quinacridone pigment, isoindoline pigment, threne pigment and perylene pigment; an extender pigment such as clay, kaolin, baryta, barium sulfate, barium carbonate, calcium carbonate, silica, alumina white and talc; an effect pigment such as aluminum flake and mica flake; etc. are preferred.
  • In the aqueous intermediate coating composition (A), the pigment may be blended as a powder in the coating composition, or after the pigment is mixed and dispersed with a part of the resin component to prepare a pigment dispersion in advance, the pigment dispersion may be mixed together with the remaining resin component or other components to form a coating composition. In preparing the pigment dispersion, conventional coating composition additives such as antifoaming agent, dispersant and surface regulator may be used, if desired. From the viewpoint of dispersibility, the pigment above is preferably used as a powder having an average particle diameter of 0.01 μm to 6 μm.
  • As for the content of the pigment (F), from the viewpoint of satisfying both the chipping resistance and the adhesive strength when bonding to a member, PWC (Pigment Weight Content) is preferably from 40% to 60%, more preferably from 45% to 55%.
    • <<Organic Solvent (G)>>
  • Examples of the organic solvent (G) include a hydrocarbon-based solvent such as hexane, heptane, xylene and toluene; esters such as ethyl acetate and butyl acetate; an ether-based solvent such as ethylene glycol monomethyl ether; an alcohol-based solvent such as ethanol, propanol and 2-ethylhexyl alcohol; a ketone-based solvent such as methyl ethyl ketone and methyl isobutyl ketone; an aromatic hydrocarbon-based solvent such as SWASOL 310 and SWASOL 1000 (produced by Cosmo Oil Co., Ltd., SWASOL is a registered trademark); an aliphatic hydrocarbon-based solvent; an alicyclic hydrocarbon-based solvent; and an amide-based solvent. One of these organic solvents may be used alone, or two or more thereof may be used in combination.
  • In the aqueous intermediate coating composition (A), the content of the organic solvent (G) is usually from 20 mass % to 50 mass %, preferably on the order of 25 mass % to 40 mass %.
  • In the aqueous intermediate coating composition (A), a curing catalyst may be used from the viewpoint of enhancing the curability. As the curing catalyst, a sulfonic acid such as paratoluenesulfonic acid, dodecylbenzenesulfonic acid and dinonylnaphthalenesulfonic acid; a neutralized salt of the sulfonic acid with amine; a neutralized salt of a phosphoric acid ester compound with amine; etc., may be used.
  • Specific examples of the curing catalyst include an organic metal catalyst such as tin octylate, dibutyltin di(2-ethylhexanoate), dioctyltin di(2-ethylhexanoate), dioctyltin diacetate, dibutyltin dilaurate, dibutyltin oxide, dioctyltin oxide, zinc 2-ethylhexanoate and zinc octylate; and a tertiary amine.
  • Furthermore, in the aqueous intermediate coating composition (A), various additives such as pigment dispersant, antifoaming agent, antioxidant, ultraviolet absorber, light stabilizer, surface regulator and gloss control agent may be appropriately blended, if desired. The aqueous intermediate coating composition (A) may be prepared by mixing and dispersing the above-described components. The solids content during coating is preferably adjusted to a range of preferably 45 mass % to 75 mass %, particularly preferably from 50 mass % to 70 mass %.
  • The aqueous intermediate coating composition (A) may be adjusted to a viscosity appropriate for the coating by adding an organic solvent and then applied and coated, if desired, by a conventional method such as rotary atomization coating, air spray or airless spray. From the viewpoint of smoothness, finish, etc. of the coated film, the coating composition may be applied to have a film thickness of usually 10 μm to 40 μm, preferably from 25 μm to 40 μm, based on the cured coated film.
  • The aqueous intermediate coated film obtained by applying the intermediate coating composition (A) can be cured per se, in the case of a baking drying, usually at a temperature of about 120° C. to about 180° C.
  • In the method for forming the multilayer coated film, the cured intermediated coated film after heat-curing the coated film (intermediate coated film) formed by the aqueous intermediate coating composition (A) has an elongation at break at 20° C. of 20% to 30%, a Young's modulus of 5,000 kgf/cm2 to 6,000 kgf/cm2, and a Tukon hardness of 4 to 6. When the elongation at break, Young's modulus and Tukon hardness fall within the ranges above, both the chipping resistance and the adhesion to glass member can be satisfied.
  • The physical values above are physical values of a cured coated film cured under the heating conditions that the thickness of the intermediate coated film is 50 μm and the coated film is kept at 140° C. for 18 minutes.
  • The elongation at break and the Young's modulus are values obtained from applying the aqueous intermediate coating composition (A) onto a glass plate to have a film thickness of 50 μm based on the cured coated film, curing the coated film by heating under the conditions of keeping it at 140° C. for 18 minutes, then separating the coated film from the glass plate, cutting the coated film into a strip shape of 20 mm in length and 5 mm in width, and measuring the strip at a tensile speed of 4 mm/min in the longitudinal direction at 20° C. by means of “TENSILON UTM-II-20” (trade name, manufactured by Orientec Inc., TENSILON is a registered trademark).
  • The elongation at break is the ratio of an increment of length when the film is broken, to the original length before test. The Young's modulus is the rising edge slope of a stress-strain curve.
  • The Tukon hardness is the value measured using TUKON (manufactured by American Chain & Cable Company, micro hardness tester) after a test coated plate prepared by applying the aqueous intermediate coating composition (A) onto an electrodeposited plate to have a film thickness of 30 μm based on the cured coated film and curing the coated film by heating under the conditions of keeping the coated film at 140° C. for 18 minutes is allowed to stand in a constant-temperature room at 20° C. for 4 hours.
  • For adjusting the above-described elongation at break, there is, for example, a method of adjusting the weight average molecular weight of the hydroxyl group-containing acrylic resin (a1) or adjusting the ratio of the hydroxyl group-containing acrylic resin (a1) to the polyurethane resin (a2).
  • For adjusting the above-described Young's modulus, there is, for example, a method of adjusting the weight average molecular weight of the hydroxyl group-containing acrylic resin (a1) or adjusting the ratio of the hydroxyl group-containing acrylic resin (a1) to the polyurethane resin (a2).
  • For adjusting the above-described Tukon hardness, there is, for example, a method of adjusting the glass transition temperature (Tg) of the hydroxyl group-containing acrylic resin (a1).
    • <Step (2)>
  • In Step (2), after preheating the intermediate coated film formed in step (1), an aqueous base coating composition (B) is applied to the intermediate coated film to form a base coated film. The aqueous base coating composition (B) is a coating composition for imparting a design property to the multilayer coated film and enhancing the design property and depth feeling by lamination with the intermediate coated film.
  • The preheating temperature is preferably from 40 to 100° C., more preferably from 50 to 90° C., still more preferably from 60 to 80° C. The preheating time is preferably from 30 seconds to 15 minutes, more preferably from 1 to 10 minutes, still more preferably from 2 to 5 minutes.
  • Before applying the aqueous base coating composition (B), the solid content percentage of the intermediate coated film is preferably adjusted to fall within the range of usually from 70 to 100 mass %, preferably from 80 to 100 mass %, more preferably from 90 to 100 mass %, by performing the preheating above.
  • As for the aqueous base coating composition (B), first, the case where the base coated film is a coated film taking on a solid color causing no change in the hue depending on the observation angle, is described. In this case, the base coated film can be formed by applying an aqueous colored base coating composition.
  • The aqueous colored base coating composition usually contains a color pigment. Specific examples of the color pigment include an organic pigment such as azo-based pigment, quinacridone-based pigment, diketopyrrolopyrrole-based pigment, perylene-based pigment, perinone-based pigment, benzimidazolone-based pigment, isoindoline-based pigment, isoindolinone-based pigment, azo metal chelate-based pigment, phthalocyanine-based pigment, indanthrone-based pigment, dioxazine-based pigment, threne-based pigment and indigo-based pigment; a metal oxide pigment such as titanium oxide pigment; and a carbon black pigment, and one of these pigments may be used alone, or two or more thereof may be used in combination.
  • From the viewpoint of brightness, etc. of the multilayer coated film, the blending amount of the color pigment in the aqueous colored base coating composition is usually from 0.01 mass % to 150 mass %, preferably from 0.05 mass % to 120 mass %, relative to the total resin solids content in the aqueous colored base coating composition. The color pigment to be blended in the aqueous colored base coating composition may be blended as a powder in the coating composition, but after the color pigment is mixed and dispersed with a part of the resin component to prepare a pigment dispersion in advance, the pigment dispersion may be mixed together with the remaining resin component or other components to form a coating composition. In preparing the pigment dispersion, conventional coating composition additives such as antifoaming agent, dispersant and surface regulator may be used, if desired.
  • The aqueous colored base coating composition may usually contain a resin component as a vehicle. Specific examples of the resin component include those in which a base resin such as acrylic resin, polyester resin, alkyd resin and urethane resin, having a crosslinking functional group such as hydroxyl group, is used in combination with a crosslinking agent such as melamine resin, urea resin and polyisocyanate compound (including a blocked form), and these are used after being dissolved or dispersed in a solvent such as organic solvent and/or water.
  • Furthermore, in the aqueous colored base coating composition, a solvent such as water or organic solvent, various additives such as dispersant, antisettling agent, curing catalyst, antifoaming agent, antioxidant, ultraviolet absorber, surface regulator and rheology control agent, an extender pigment, etc. may be appropriately blended, if desired.
  • The aqueous colored base coating composition can be prepared by mixing and dispersing the above-described components. The solids content during coating is preferably adjusted to a range of usually 12 mass % to 60 mass %, preferably from 15 mass % to 50 mass %, based on the coating composition.
  • The aqueous colored base coating composition may be adjusted to a viscosity appropriate for the coating by adding water, an organic solvent, etc. and then applied by electrostatic coating, air spray, airless spray or other methods and from the viewpoint of smoothness, the film thickness is usually from 5 μm to 30 μm, preferably from 5 μm to 25 μm, more preferably from 10 μm to 25 μm, based on the cured coated film.
  • Next, the case where the base coated film is a coated film taking on a metallic color causing a change in the hue depending on the observation angle, is described. In this case, the base coated film can be formed by applying an aqueous metallic base coating composition as the aqueous base coating composition (B).
  • The aqueous metallic base coating composition usually contains a flake-like effect pigment with the purpose of imparting a particle feeling to the coated film. As the flake-like effect pigment, one kind or a combination of two or more kinds may be appropriately selected from light reflecting pigments and light interference pigments.
  • Specific examples of the light reflecting pigment include a flake-like metal pigment such as aluminum, copper, nickel alloy and stainless steel, a flake-like metal pigment in which the surface is coated with metal oxide, a flake-like metal pigment in which color pigment is chemically adsorbed or bonded to the surface, and a flake-like aluminum pigment in which an aluminum oxide layer is formed on the surface by inducing an oxidation reaction. Among these, from the viewpoint of particle feeling or finish appearance, a flake-like aluminum pigment may be suitably used.
  • The flake-like aluminum pigment is usually produced by grinding and milling aluminum in the presence of a liquid grinding medium with use of a grinding aid in a ball mill or an attritor mill. As the grinding aid, a higher fatty acid such as oleic acid, stearic acid, isostearic acid, lauric acid, palmitic acid and myristic acid, an aliphatic amine, an aliphatic amide, an aliphatic alcohol, etc. may be used. As the liquid grinding medium, an aliphatic hydrocarbon such as mineral spirit may be used.
  • The flake-like aluminum pigment can be roughly classified into a leafing type and a non-leafing type depending on the kind of the grinding aid. When the leafing-type pigment is blended in the coating composition, flakes are arranged on the surface of the coated film (leafing) obtained by applying the coating composition, giving a finish with strong metallic feeling, and since the pigment has heat-reflecting action and exerts rust-preventing power, this type is often used for various building materials including a tank, a duct, pipings and roofing of production equipment, etc. A flake-like aluminum pigment of a leafing type may be used, but in the case of using a flake-like aluminum pigment of this type, attention is required, because although it varies depending on the blending amount, the pigment may completely hide the surface by the effect of surface tension of the grinding aid in the process of forming the coated film and a particle feeling may not be expressed. From this viewpoint, a flake-like aluminum pigment of a non-leafing type is preferably used.
  • As for the size of the flake-like aluminum pigment, from the viewpoint of finish appearance, highlight brightness and particle feeling of the multilayer coated film, a pigment having an average particle diameter of usually 8 μm to 25 μm, preferably from 10 μm to 18 μm, is preferably used, and the thickness is preferably from 0.2 μm to 1.0 μm. The particle diameter and thickness as used herein indicate the median diameter in a volume-basis particle size distribution measured by the laser diffraction scattering method by using a Microtrac particle size distribution measuring apparatus, MT3300 (trade name, manufactured by Nikkiso Co., Ltd.). If the average particle diameter is controlled to equal to or less than the upper limit above, the particle feeling of the coated film obtained can be avoided from becoming excessive, and this is advantageous in terms of design property, whereas if it is controlled to equal to or more than the lower limit, the particle feeling can be sufficient.
  • In the aqueous metallic base coating composition, a light interference pigment may be used as the flake-like effect pigment. As the light interference pigment, specifically, a pigment obtained by coating a semitransparent substrate, such as natural mica, artificial mica, alumina flake, silica flake and glass flake, with a metal oxide may be used.
  • The metal oxide-coated mica pigment is a pigment in which the substrate is natural mica or artificial mica and the substrate surface is coated with a metal oxide. The natural mica is a flake-like substrate obtained by grinding mica from ore, and the artificial mica is synthesized by heating an industrial raw material, such as SiO2, MgO, Al2O3, K2SiF6 or Na2SiF6, melting the raw material at a high temperature of about 1,500° C., and cooling the melt for crystallization. In this mica, as compared with natural mica, the impurity content is small, and the size or thickness is uniform. Specifically, fluorine-based mica (KMg3AlSi3O10F2), potassium tetrasilicon mica (KMg25AlSi4O10F2), sodium tetrasilicon mica (NaMg25AlSi4O10F2), Na taeniolite (NaMg2LiSi4O10F2), LiNa taeniolite (LiNaMg2LiSi4O10F2), etc. are exemplified. Examples of the metal oxide coat include titanium oxide and iron oxide. An interference color can be developed by the metal oxide coat.
  • The metal oxide-coated alumina flake pigment is a pigment in which the substrate is alumina flake and the substrate surface is coated with a metal oxide. The alumina flake means a flake-like (foil-like) aluminum oxide and is colorless and transparent. The alumina flake need not be an aluminum oxide single component and may contain an oxide of other metals. Examples of the metal oxide coat include titanium oxide and iron oxide. An interference color can be developed by the metal oxide coat.
  • The metal oxide-coated silica flake pigment is a pigment in which flake-like silica as a substrate having smooth surface and uniform thickness is coated with a metal oxide having a refractive index different from that of the substrate. Examples of the metal oxide coat include titanium oxide and iron oxide. An interference color can be developed by the metal oxide coat.
  • The metal oxide-coated glass flake pigment is a pigment in which a flake-like glass substrate is coated with a metal oxide, and since the substrate surface is smooth, strong light reflection is caused to express a particle feeling. Examples of the metal oxide coat include titanium oxide and iron oxide. An interference color can be developed by the metal oxide coat.
  • The light interference pigment may be subjected to a surface treatment so as to enhance the dispersibility, water resistance, chemical resistance, weather resistance, etc.
  • As for the size of the light interference pigment, in the case of a light interference pigment using natural mica, artificial mica, alumina flake or silica flake as the substrate, from the viewpoint of finish appearance or particle feeling of the coated film, a pigment having an average particle diameter of usually 5 μm to 30 μm, preferably from 7 μm to 25 μm, may be suitably used.
  • In the case of a light interference pigment using glass flake as the substrate, from the viewpoint of particle feeling of the coated film, a pigment having an average particle diameter of usually 15 μm to 100 μm, preferably from 17 μm to 45 μm, may be suitably used. A light interference pigment having a thickness of usually 0.05 μm to 7.0 μm, preferably from 0.1 μm to 3 μm, is suitably used.
  • The particle diameter and thickness as used herein indicate the median diameter in a volume-basis particle size distribution measured by the laser diffraction scattering method by using a Microtrac particle size distribution measuring apparatus, MT3300 (trade name, manufactured by Nikkiso Co., Ltd.).
  • If the average particle diameter is controlled to equal to or less than the upper limit above, the particle feeling of multilayer coated film, developed by the light interference pigment, can be prevented from becoming excessive, and this is advantageous in terms of design property, whereas if it is controlled to equal to or more than the lower limit, the particle feeling can be sufficient.
  • From the viewpoint of finish appearance or particle feeling of the coated film obtained, the content of the flake-like effect pigment in the aqueous metallic base coating composition is, in total, preferably from 0.01 mass % to 25 mass %, more preferably from 0.01 mass % to 15 mass %, further preferably from 0.05 mass % to 5 mass %, relative to the total solid content of the resin composition in the coating composition.
  • The aqueous metallic base coating composition may contain a color pigment with the purpose of adjusting the hue and brightness of the coated film obtained. Specific examples of the color pigment include an inorganic pigment, e.g., a transparent iron oxide pigment, a composite oxide pigment such as titanium yellow, a titanium oxide pigment containing fine-particle titanium oxide, and a carbon black pigment; and an organic pigment such as azo-based pigment, quinacridone-based pigment, diketopyrrolopyrrole-based pigment, perylene-based pigment, perinone-based pigment, benzimidazolone-based pigment, isoindoline-based pigment, isoindolinone-based pigment, azo-metal chelate pigment, phthalocyanine-based pigment, indanthrone-based pigment, dioxazine-based pigment, threne-based pigment and indigo-based pigment. One of these may be used alone, or two or more thereof may be used in combination.
  • The color pigment may be blended as a powder in the coating composition, or after the color pigment is mixed and dispersed with a part of the resin composition to prepare a pigment dispersion in advance, the pigment dispersion may be mixed together with the remaining resin component or other components to form a coating composition. In preparing the pigment dispersion, conventional coating composition additives such as antifoaming agent, dispersant and surface regulator may be used, if desired.
  • In the case of incorporating a color pigment into the aqueous metallic base coating composition, from the viewpoint of brightness, etc. of the multilayer coated film, the blending amount thereof is usually from 0.01 mass % to 10 mass %, preferably from 0.01 mass % to 5 mass %, relative to the total solid content of the resin composition in the coating composition.
  • The aqueous metallic base coating composition usually contains a resin composition as a vehicle-forming component. Specific examples of the resin composition include those in which a base resin such as acrylic resin, polyester resin, alkyd resin and urethane resin, having a crosslinking functional group such as hydroxyl group, is used in combination with a crosslinking agent such as melamine resin, urea resin and polyisocyanate compound (including a blocked form), and these are used after being dissolved or dispersed in a solvent such as organic solvent and/or water.
  • Furthermore, in the aqueous metallic base coating composition, a solvent such as water or organic solvent, various additives such as pigment dispersant, curing catalyst, antifoaming agent, antioxidant, ultraviolet absorber and surface regulator, a gloss control agent, an extender pigment, etc. may be appropriately blended, if desired.
  • The aqueous metallic base coating composition is prepared by mixing and dispersing the above-described components. The solid content during coating is preferably adjusted to a range of usually 12 mass % to 60 mass %, preferably from 15 mass % to 50 mass %, based on the coating composition.
  • The aqueous metallic base coating composition may be adjusted to a viscosity appropriate for the coating by adding water or an organic solvent and then applied by a conventional method such as rotary atomization coating, air spray or airless spray.
  • From the viewpoint of smoothness, etc. of the coated film, the coating composition is preferably applied to have a film thickness of usually 10 μm to 25 μm based on the cured coated film and may be applied to have a film thickness of more preferably from 10 μm to 20 μm, still more preferably from 13 μm to 17 μm.
  • In the present specification, the aqueous coating composition is a term contrasted with an organic solvent-based coating composition and in general, means a coating composition obtained by dispersing and/or dissolving a coated film-forming resin, a pigment, etc. in water or a medium containing water as the main component (aqueous medium).
  • The base resin of the resin composition of the aqueous base coating composition (B) preferably has an acid group, and in the case of dispersion in water, from the viewpoint of enhancing water dispersibility, the acid group is preferably neutralized with a neutralizer so as to facilitate mixing and dispersion in water.
  • The neutralizer is not particularly limited as long as it can neutralize an acid group, and examples thereof include a basic compound such as sodium hydroxide, potassium hydroxide, trimethylamine, 2-(dimethylamino)ethanol, 2-amino-2-methyl-1-propanol, triethylamine and aqueous ammonia.
  • The base coated film obtained by applying the aqueous base coating composition (B) can be cured per se, in the case of a baking drying type, usually at a temperature of about 50° C. to about 180° C., and in the case of a normal temperature drying type or a forced drying type, can be cured usually at a temperature from room temperature to about 80° C.
    • <Step (3)>
  • In Step (3), a base coated film obtained by applying the aqueous base coating composition (B) as above is preheated under heating conditions causing substantially no curing of the coated film, and a clear coating composition (C) is applied to the base coated film to form a clear coated film.
  • The preheating temperature is preferably from 40 to 100° C., more preferably from 50 to 90° C., still more preferably from 60 to 80° C. The preheating time is preferably from 30 seconds to 15 minutes, more preferably from 1 to 10 minutes, still more preferably from 2 to 5 minutes.
  • Before applying the clear coating composition (C), the solid content percentage of the base coated film is suitably adjusted to fall within the range of usually from 70 to 100 mass %, preferably from 80 to 100 mass %, more preferably from 90 to 100 mass %, by performing the preheating above.
    • <<Clear Coating Composition (C)>>
  • In the method, the clear coating composition (C) is a clear coating composition containing the hydroxyl group-containing acrylic resin (c1) and the allophanate group-containing polyisocyanate compound (c2).
  • <<Hydroxyl Group-Containing Acrylic Resin (c1)>>
  • The hydroxyl group-containing acrylic resin (c1) can be produced, for example, by (co)polymerizing at least one unsaturated monomer component having a hydroxyl group-containing unsaturated monomer and, depending on the case, further having other unsaturated monomers copolymerizable with the monomer above, under normal conditions.
  • The hydroxyl group-containing unsaturated monomer is a compound having at least one hydroxyl group and at least one polymerizable unsaturated bond per molecule, and examples thereof may include what is described in an explanation column of the hydroxyl group-containing acrylic resin (a1) above.
  • As other unsaturated monomers copolymerizable with the above-described hydroxyl group-containing unsaturated monomer, for example, what is described in an explanation column of the hydroxyl group-containing acrylic resin (a1) above may be used.
  • The hydroxyl value of the hydroxyl group-containing acrylic resin (c1) is preferably from 120 mg KOH/g to 200 mg KOH/g, more preferably from 130 mg KOH/g to 200 mg KOH/g, particularly more preferably from 140 mg KOH/g to 200 mg KOH/g from the viewpoint of satisfying both the scratch resistance and the water resistance.
  • The weight average molecular weight of the hydroxyl group-containing acrylic resin (c1) is preferably from 5,000 to 30,000, more preferably from 5,000 to 20,000, still more preferably from 8,000 to 20,000. By setting the weight average molecular weight to 5000 or more, deterioration of coating film performance such as acid resistance is prevented, and in addition, by setting it to 30,000 or less, it is possible to prevent deterioration of the finished appearance accompanying a decrease in the smoothness of the coating film, therefore it is preferable.
  • The glass transition temperature of the hydroxyl group-containing acrylic resin (c1) is preferably from −30° C. to 30° C., more preferably from −20° C. to 20° C. When the glass transition temperature is −30° C. or more, sufficient coating film hardness can be obtained, and when it is 30° C. or less, deterioration of the coated surface smoothness and crack resistance of the coating film can be prevented.
  • Furthermore, the hydroxyl group-containing acrylic resin (c1) also includes a so-called urethane-modified acrylic resin.
  • The hydroxyl group-containing acrylic resin (c1) may be used alone, or two or more thereof may be used in combination.
  • In the coating composition, resins other than the hydroxyl group-containing acrylic resin (c1) may also be used in combination, as the base resin, if desired. Accordingly, the coating composition includes a resin other than the hydroxyl group-containing acrylic resin (c1) as the base resin. Specifically, examples thereof include polyester resin, polyether resin, polyurethane resin and the like, and preferred examples thereof include hydroxyl group-containing polyester resin and a hydroxyl group-containing polyurethane resin.
  • The hydroxyl group-containing polyester resin (C) can be synthesized, for example, by an esterification reaction of a polybasic acid and a polyhydric alcohol in a usual manner. The polybasic acid is a compound having two or more carboxyl groups per molecule and examples thereof include phthalic acid, isophthalic acid, terephthalic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, tetrahydrophthalic acid, hexahydrotrimellitic acid, maleic acid, fumaric acid, itaconic acid, trimellitic acid, pyromellitic acid, and anhydrides thereof. The polyhydric alcohol is a compound having two or more hydroxyl groups per molecule and examples thereof include glycols such as ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2,2-dimethyl-1,3-propanediol, neopentyl glycol, 1,9-nonanediol, 1,4-cyclohexanediol, neopentyl glycol and hydroxypivalic acid-neopentyl glycol ester, 2-butyl-2-ethyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2,2,4-trimethylpentanediol, diols such as hydrogenated bisphenol A, and a trihydric or higher polyhydric polyol composition such as trimethylolpropane, trimethylolethane, glycerin, and pentaerythritol, and a hydroxycarboxylic acid such as 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, 2,2-dimethylolpentanoic acid, 2,2-dimethylolhexanoic acid and 2,2-dimethyloloctanoic acid.
  • An α-olefin epoxide such as propylene oxide or butylene oxide, a monoepoxy compound such as CARDURA E10 (produced by Japan Epoxy Resin Co., Ltd., trade name, a glycidyl ester of a synthetic hyperbranched saturated fatty acid), etc. is reacted with an acid, and the compound thereof may be introduced into the polyester resin.
  • In the case of introducing a carboxyl group into the polyester resin, the carboxyl group may be introduced, for example, by adding an acid anhydride to a hydroxyl group-containing polyester to cause half-esterification.
  • The hydroxyl value of the hydroxyl group-containing polyester resin is preferably from 100 mg KOH/g to 200 mg KOH/g, particularly preferably from 120 mg KOH/g to 180 mg KOH/g. The weight average molecular weight of the hydroxyl group-containing polyester resin is preferably from 2,500 to 40,000, more preferably from 5,000 to 30,000.
  • As the hydroxyl group-containing polyurethane resin, examples thereof include a hydroxyl group-containing polyurethane resin obtained by reacting a polyol and a polyisocyanate.
  • As the polyol, examples thereof as low-molecular-weight ones include divalent alcohol such as ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, and hexamethylene glycol; and trihydric alcohol such as trimethylolpropane, glycerin, and pentaerythritol. In addition, examples thereof as high-molecular-weight ones include polyether polyol, polyester polyol, acrylic polyol, and epoxy polyol. As the polyether polyol, examples thereof include polyethylene glycol, polypropylene glycol, and polytetramethylene glycol. As the polyester polyol, examples thereof include alcohol such as the divalent alcohol, dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, and neopentyl glycol; polycondensate with dibasic acid such as adipic acid, azelaic acid, sebacic acid and the like; lactone type ring opening polymer polyol such as polycaprolactone; polycarbonate diol. In addition, for example, carboxyl group-containing polyols such as 2,2-dimethylolpropionic acid and 2,2-dimethylolbutanoic acid may also be used.
  • As the polyisocyanate to be reacted with the polyol, examples thereof include an aliphatic polyisocyanate compound such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, dimer acid diisocyanate, and lysine diisocyanate; and buret type adduct and isocyanurate ring adduct of polyisocyanate thereof; an alicyclic diisocyanate compound such as isophorone diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), methylcyclohexane-2,4- (or -2,6-) diisocyanate, 1,3- (or 1,4-) di (isocyanatomethyl) cyclohexane, 1,4-cyclohexane diisocyanate, 1,3-cyclopentane diisocyanate, and 1,2-cyclohexane diisocyanate; and buret type adduct and isocyanurate ring adduct of polyisocyanate thereof; an aromatic diisocyanate compound such as xylylene diisocyanate, metaxylylene diisocyanate, tetramethylxylylene diisocyanate, tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, 1,4-naphthalene diisocyanate, 4,4-toluidine diisocyanate, 4,4′-diphenyl ether diisocyanate, (m- or p-) phenylene diisocyanate, 4,4′-biphenylene diisocyanate, 3,3′-dimethyl-4,4′-biphenylene diisocyanate, bis (4-isocyanatophenyl) sulfone, isopropylidenebis (4-phenylisocyanate); and buret type adduct and isocyanurate ring adduct of polyisocyanate thereof; polyisocyanate compound having three or more isocyanate groups in one molecule such as triphenylmethane-4,4′,4″-triisocyanate, 1,3,5-triisocyanatobenzene, 2,4,6-triisocyanatotoluene, 4,4′-dimethyldiphenylmethane-2,2 ‘, 5,5’-tetraisocyanate; and buret type adduct and isocyanurate ring adduct of polyisocyanate thereof.
  • The hydroxyl value of the hydroxyl group-containing polyurethane resin is preferably from 80 mg KOH/g to 200 mg KOH/g, particularly preferably from 100 mg KOH/g to 180 mg KOH/g. The weight average molecular weight of the hydroxyl group-containing polyurethane resin is preferably from 2,500 to 40,000, more preferably from 5,000 to 30,000. The glass transition temperature of the hydroxyl group-containing polyurethane resin is preferably from −40° C. to 85° C., more preferably from −30° C. to 80° C.
  • When a resin other than the hydroxyl group-containing acrylic resin (c1) (more specifically, polyester resin, polyether resin, polyurethane resin, etc.) is used in combination, the resin other than the hydroxyl group-containing acrylic resin (c1) is preferably 100 mass % or less, more preferably from 10 mass % to 50 mass %, relative to the total solid content of the hydroxyl group-containing acrylic resin (c 1).
  • [Allophanate Group-Containing Polyisocyanate Compound (c2)]
  • The allophanate group-containing polyisocyanate compound (c2) is a compound obtained by subjecting a polyisocyanate selected from aliphatic polyisocyanate, alicyclic polyisocyanate, aromatic polyisocyanate and the like to an allophanatizing esterification reaction by a known method.
  • Examples of the aliphatic polyisocyanate include a diisocyanate (C2-16 alkane diisocyanate such as trimethylene diisocyanate, 1,2-propylene diisocyanate, tetramethylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, and 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate; and 2,6-diisocyanatomethylcaproate); and a polyisocyanate (such as lysine ester triisocyanate, and C6-20 alkane triisocyanate such as 1,4,8-triisocyanatooctane, 1,6,11-triisocyanatoundecane, 1,8-diisocyanato-4-isocyanatomethyloctane, 1,3,6-triisocyanatohexane and 2,5,7-trimethyl-1,8-diisocyanaato-5-isocyanatomethyloctane).
  • Examples of the alicyclic polyisocyanate include a diisocyanate (such as 1,3-cyclopentene diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (common name: isophorone diisocyanate), 4,4′-methylenebis (cyclohexylisocyanate), methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 1,3- or 1,4-bis(isocyanatomethyl)cyclohexane (common name: hydrogenated xylylene diisocyanate) or a mixture thereof and norbornane diisocyanate); and a polyisocyanate (triisocyanate such as 1,3,5-triisocyanatocyclohexane, 1,3,5-trimethylisocyanatocyclohexane, 2-(3-isocynatopropyl)-2,5-di(isocyanatomethyl)-bicyclo[2.2.1]heptane, 2-(3-isocyanatopropyl)-2,6-di(isocyanatomethyl)-bicyclo[2.2.1]heptane, 3-(3-isocyanatopropyl)-2,5-di(isocyanatomethyl)-bicyclo[2.2.1]heptane, 5-(2-isocyanatoethyl)-2-isocyanatomethyl-3-(3-isocyanatopropyl)-bicyclo[2.2.1]heptane, 6-(2-isocyanatoethyl)-2-isocyanatomethyl-3-(3-isocyanatopropyl)-bicyclo[2.2.1]heptane, 5-(2-isocyanatoethyl)-2-isocyanatomethyl-2-(3-isocyanatopropyl)-bicyclo[2.2.1]-heptane and 6-(2-isocyanatoethyl)-2-isocyanatomethyl-2-(3-isocyanatopropyl)-bicyclo[2.2.1]heptane.
  • Examples of the aromatic polyisocyanate include a diisocyanate (such as 1,3- or 1,4-xylylene diisocyanate or a mixture thereof, ω,ω′-diisocyanato-1,4-diethylbenzene, and 1,3- or 1,4-bis(1-isocyanato-1-methylethyl)benzene (common name: tetramethylxylylene diisocyanate) or a mixture thereof, m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, 2,4′- or 4,4′-diphenylmethane diisocyanate or a mixture thereof, 2,4- or 2,6-tolylene diisocyanate or a mixture thereof, 4,4′-toluidine diisocyanate and 4,4′-diphenylether diisocyanate); a polyisocyanate (for example, triisocyanate such as 1,3,5-triisocyanatomethylbenzene; triisocyanate such as triphenylmethane-4,4′,4″-triisocyanate, 1,3,5-triisocyanatebenzene, 2,4,6-triisocyanatetoluene; and for example, tetraisocyanate such as 4,4′-diphenylmethane-2,2′,5,5′-tetraisocyanate).
  • Among these, the allophanate group-containing polyisocyanate compound (c2) of the aliphatic polyisocyanate is particularly preferable from the viewpoints of scratch resistance, hardness, yellowing resistance and the like of the coated film obtained.
  • Among the aliphatic polyisocyanates, hexamethylene diisocyanate is particularly preferable from the viewpoints of scratch resistance, hardness, yellowing resistance and the like of the coated film obtained.
  • The clear coating composition (C) may contain a polyisocyanate compound other than the allophanate group-containing polyisocyanate compound (c2), if desired.
  • Examples thereof include a biuret group-containing polyisocyanate compound obtained by biuretizing a polyisocyanate selected from an aliphatic polyisocyanate, an alicyclic polyisocyanate, an aromatic polyisocyanate, and the like by a known method; aliphatic polyisocyanates such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, dimer acid diisocyanate and lysine diisocyanate; isocyanurate ring adduct and uretdione type adducts of the aliphatic polyisocyanates thereof; alicyclic diisocyanates such as isophorone diisocyanate, 4,4′-methylenebis (cyclohexylisocyanate), and methylcyclohexane-2,4- or -2,6-diisocyanate; isocyanurate ring adduct of the alicyclic diisocyanates thereof; an aromatic diisocyanate compound such as xylylene diisocyanate, tetramethylxylylene diisocyanate, tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate (MDI), 1,5-naphthalene diisocyanate, and 1,4-naphthalene diisocyanate; isocyanurate ring adduct of the aromatic diisocyanate thereof; hydrogenated MDI and derivatives of hydrogenated MDI; a urethanized adduct obtained by reacting a hydroxyl group of a polyol such as ethylene glycol, propylene glycol, 1,4-butylene glycol, dimethylolpropionic acid, polyalkylene glycol, trimethylolpropane and hexanetriol, with a polyisocyanate compound in such a ratio that an isocyanate group is an excessive amount; isocyanurate ring adduct of the urethanized adduct thereof.
  • The amount of the allophanate group-containing polyisocyanate compound (c2) used is that an equivalent ratio of NCO/OH, i.e. the isocyanate group (NCO) contained therein to the hydroxyl group (OH) in the clear coating composition (C) is preferably from 0.1 to 2.0, more preferably from 0.2 to 1.7, particularly more preferably from 0.6 to 1.5.
  • When the clear coating composition (C) contain a polyisocyanate compound other than the allophanate group-containing polyisocyanate compound (c2), an equivalent ratio of NCO/OH, i.e. total isocyanate groups (NCO) contained in the allophanate group-containing polyisocyanate compound (c2) and polyisocyanate compound other than the allophanate group-containing polyisocyanate compound (c2) to the hydroxyl group (OH) in the clear coating composition (C), is preferably from 0.5 to 2.0, more preferably from 0.6 to 1.7, particularly more preferably from 0.7 to 1.5.
  • The clear coating composition (C) may contain, if desired, a color pigment, an effect pigment, a dye, etc. to an extent not impairing transparency and may further appropriately contain an extender pigment, a UV absorber, an antifoaming agent, a thickener, a rust-preventive agent, a surface conditioner, an organic solvent, etc.
  • The clear coating composition (C) can be applied to the coated film surface of the aqueous base coating composition (B) by a method known per se, such as airless spray, air spray and rotary atomizing coater, and static electricity may be applied during application of the coating composition. The coated film thickness may be made to fall within the range of usually from 10 to 60 μm, preferably from 25 to 50 μm, in terms of cured film thickness.
  • In this specification, the number average molecular weight and the weight average molecular weight are a value calculated from a chromatogram measured by gel permeation chromatography, based on the molecular weight of standard polystyrene. As for the gel permeation chromatograph, “HLC8120GPC” (manufactured by Tosoh Corporation) was used. The measurement was performed using four columns of “TSKgel G-4000HXL”, “TSKgel G-3000HXL”, “TSKgel G-2500HXL” and “TSKgel G-2000HXL” (trade names, all manufactured by Tosoh Corporation) under the conditions of mobile phase: tetrahydrofuran, measurement temperature: 40° C., flow velocity: 1 cc/min, and detector: RI.
    • <Step (4)>
  • In Step (4), the intermediate coated film, the base coated film and the clear coated film formed in the above steps (1) to (3), respectively, are heat-cured. The clear coated film formed by applying the clear coating composition (C) is usually heat-cured simultaneously with the uncured base coated film.
  • The heating may be performed by a normal heating method of a coated film such as hot-air heating, infrared heating or high-frequency heating. The heating temperature is preferably from 60° C. to 180° C., more preferably from 110° C. to 170° C., still more preferably from 130° C. to 160° C. The heating time is not particularly limited but is preferably from 10 minutes to 90 minutes, more preferably from 15 minutes to 60 minutes, still more preferably from 15 minutes to 30 minutes.
  • Before heat-curing, preheating may be appropriately performed. The preheating temperature is preferably from 40° C. to 110° C., more preferably from 50° C. to 110° C., and the preheating time is preferably from 30 seconds to 15 minutes, more preferably from 1 minute to 10 minutes.
  • By this heating, the multilayer coated film including an intermediate coated film, a base coated film and a clear coated film layer can be cured.
  • In the multilayer coated film obtained by the method, from the viewpoint of finish appearance, the film thickness is preferably from 70 μm to 120 μm, more preferably from 80 μm to 100 μm, based on the cured coated film.
  • In the method, in a part of an automotive body (for example, a portion to which front glass or rear glass is fixed), the following step (5) may be contained: an adhesive layer is formed on the clear coated film of the multilayer coated film including the intermediate coated film, the base coated film and the clear coated film, obtained according to the steps (1) to (4). The embodiments of the step (5) are described below.
    • <Step (5)>
  • In Step (5), in order to bond the automobile main body to a glass member, etc., an adhesive layer is formed on the clear coated film, usually in a frame shape corresponding to the shape of a glass member to be fixed.
  • As the adhesive for forming the adhesive layer, a resin composition usually used as an adhesive, a sealing agent or a coating agent, for example, urethane-based adhesives, acrylic adhesives, silicone-based adhesives, modified silicone-based adhesives, polysulfide-based adhesives, epoxy-based adhesives and PVC-based adhesives, may be used.
  • Among these, from the viewpoint of adhesion to the clear coated film and high weather resistance, a urethane-based adhesive is preferably used. The urethane-based adhesive may be sufficient if it is an adhesive having an isocyanate group, and the adhesive may be any of a thermosetting adhesive, a thermoplastic adhesive, etc. and examples thereof include an adhesive containing methylene-bis (p-phenylene diisocyanate), hexamethylene diisocyanate, 1,6-hexamethylene diisocyanate, 2,4-tolylene diisocyanate, toluene diisocyanate, 1-chlorophenyl diisocyanate, 1,5-naphthylene diisocyanate, thiodipropyl diisocyanate, ethylbenzene-α-2-diisocyanate, or 4,4′,4″-triphenylmethane triisocyanate. As for the urethane-based adhesive, either one-pack type or two-pack type may be used, but in particular, a one-pack moisture-curable urethane-based adhesive is preferably used.
  • Specific examples of the adhesive include “3740”, “3765T” and “560F” (all trade names) produced by Sunstar Inc.; “WS373”, “WS282”, “WS202” and “WS252” (all trade names) produced by Yokohama Rubber Co., Ltd.; and “58702SFL” and “58702SFH” (both trade names) produced by Dow Chemical.
  • The method for applying the adhesive is not particularly limited, but from the viewpoint of productivity, in the automotive production line, coating by a robotic painting machine is widely performed in general. As for the coating amount of the adhesive, the adhesive is preferably applied to have a film thickness of usually approximately from 3 mm to 6 mm based on the cured coated film.
  • In the case of bonding the multilayer coated film to a glass member, by the step (5), an adhesive layer is formed usually in a frame shape corresponding to the shape of a glass member to be fixed, on a part of an electrodeposition coated automotive body, a glass member such as front glass or rear window is laid thereon, and the adhesive layer is cured, whereby the glass member is fixed to the automotive body.
    • EXAMPLES
  • An aspect of the present invention is described more specifically below by referring to Examples and Comparative Examples. However, the present invention is not limited only to the following Examples. Here, both “parts” and “%” are on a mass basis, and the thickness of the coated film is based on the cured coated film.
  • <Production of Hydroxyl Group-Containing Acrylic Resin (a1)>
  • Production of Hydroxyl Group-Containing Acrylic Resin (a1-1)
  • 35 Parts of propylene glycol monopropyl ether was added to a flask, and the temperature was raised to 85° C. A mixture of 10 parts of 2-hydroxyethyl methacrylate, 20 parts of styrene, 22 parts of isobutyl methacrylate, 42 parts of n-butyl methacrylate, 6 parts of acrylic acid, 15 parts of propylene glycol monopropyl ether, and 2.0 parts of 2,2′-azobis(2,4-dimethylvaleronitrile) was added dropwise to the flask over 4 hours, and after the completion of dropwise addition, the mixture was aged for 1 hour. Subsequently, a mixture of 10 parts of propylene glycol monopropyl ether and 1 part of 2,2′-azobis(2,4-dimethylvaleronitrile) was further added dropwise to the flask over 1 hour, and after the completion of dropwise addition, the mixture was aged for 1 hour. Thereafter, 7.4 parts of diethanolamine and 13 parts of propylene glycol monopropyl ether were further added to obtain a hydroxyl group-containing acrylic resin (a1-1) having a solid content concentration of 55%. The hydroxyl group-containing acrylic resin (a1-1) obtained had a glass transition temperature of 5° C., a weight average molecular weight of 35,000, a hydroxyl value of 43 mgKOH/g, and an acid value of 47 mgKOH/g.
  • Production of Hydroxyl Group-Containing Acrylic Resins (a1-2) to (a1-6)
  • Solutions of hydroxyl group-containing acrylic resins (a1-2) to (a1-6) having a solid content concentration of 55% were obtained in the same manner as in the production of hydroxyl group-containing acrylic resin (a1-1) except that the blending formulation of the monomer mixture and the reaction temperature were changed as shown in Table 1. The glass transition temperature, weight average molecular weight, hydroxyl value and acid value of each of the hydroxyl group-containing acrylic resins are shown together in Table 1.
  • TABLE 1
    Name of hydroxyl group-containing acrylic resin (a1)
    a1-1 a1-2 a1-3 a1-4 a1-5 a1-6
    Hydroxyl group- 2-Hydroxyethyl 10 10 10 10
    containing methacrylate
    unsaturated 2-Hydroxyethyl acrylate 9 9
    monomer
    Other unsaturated Styrene 20 20 20 10 10 25
    monomers Isobutyl methacrylate 22 29 35 35 38 30
    n-Butyl acrylate 42 35 29 40 36 30
    Acrylic acid 6 6 6 6 6 6
    Polymerization 2,2′-Azobis(2,4- 2 2 2 1.5 3.5 1.5
    initiator dimethylvaleronitrile)
    Reaction temperature [° C.] 85 85 85 85 85 85
    Glass transition temperature [° C.] 5 14 21 0 10 15
    Weight average molecular weight 35,000 34,000 33,000 34,000 25,000 45,000
    Hydroxyl value [mgKOH/g] 43 43 43 44 43 44
    Acid value [mgKOH/g] 47 47 47 47 47 47
    • Production of Aqueous Intermediate Coating Composition (A)
  • Production of Aqueous Intermediate Coating Composition (A1) 36 Parts (resin solid content: 20 parts) of the hydroxyl group-containing acrylic resin (a1-1) shown in Table 1, 90 parts of “JR-806” (trade name, produced by Tayca Corporation, rutile titanium dioxide), 0.1 parts of “Carbon MA-100” (trade name, produced by Mitsubishi Chemical Corporation, carbon black), and 5 parts of deionized water were mixed and after adjusting the pH to 8.0 with 2-(dimethylamino)ethanol, the mixture was dispersed by means of a paint shaker for 30 minutes to obtain a pigment dispersion paste. Subsequently, 131 parts of the obtained pigment dispersion paste, 10 parts of the polyurethane resin (a2-1), 30 parts of hydroxyl group-containing polyester resin (a3), 30 parts of melamine resin (a4), and 10 parts of active methylene-blocked polyisocyanate compound (a5), each shown below, were uniformly mixed. Then, to the obtained mixture, “UH-752” (trade name, produced by ADEKA Co., Ltd., thickener), 2-(dimethylamino)ethanol, and deionized water were added to obtain an aqueous intermediate coating composition (Al) having a viscosity of 45 seconds as measured with Ford cup No. 4 at 20° C.
  • Production of Aqueous Intermediate Coating Compositions (A2) to (A16)
  • Aqueous intermediate coating compositions (A2) to (A16) having a viscosity of 45 seconds as measured with Ford cup No. 4 at 20° C. were obtained in the same manner as in the above production of aqueous intermediate coating composition (Al) except that respective raw materials were changed to raw materials each having the composition shown in Table 2 below. Here, the blending amount of each component is the amount (parts) of solid contents.
  • Polyurethane Resin (a2-1): “Superflex E-4800” (trade name, produced by Dai-Ichi Kogyo Seiyaku Co., Ltd., Superflex is a registered trademark, a polyurethane resin having a polyether skeleton, and glass transition temperature of −65° C.)
  • Polyurethane Resin (a2-2): “Superflex E-2000” (trade name, produced by Dai-Ichi Kogyo Seiyaku Co., Ltd., Superflex is a registered trademark, a polyurethane resin having a polyester skeleton, and glass transition temperature of −38° C.)
  • Hydroxyl Group-Containing Polyester Resin (a3): Obtained by using trimethylolpropane, cyclohexanedimethanol, isophthalic acid and adipic acid and performing an esterification reaction in a usual manner; number average molecular weight of 4,500, hydroxyl value of 120, and acid value of 10.
  • Melamine Resin (a4): Imino group-containing methyl-butyl mixed etherified melamine; weight average molecular weight of 1,200.
  • Active Methylene-Blocked Polyisocyanate Compound (a5):
  • 360 parts of “SUMIDUR N-3300” (trade name, produced by Sumika Bayer Urethane Co., Ltd., SUMIDUR being a registered trademark, polyisocyanate having an isocyanurate structure derived from hexamethylene diisocyanate, solids content of about 100%, and isocyanate group content percentage of 21.8%), 60 parts of “Uniox M-550” (trade name, produced by NOF Corporation, Uniox being a registered trademark, polyethylene glycol monomethyl ether, and average molecular weight of about 550), and 0.2 part of 2,6-di-tert-butyl-4-methylphenol were added to a reaction vessel equipped with a thermometer, a thermostat, a stirrer, a reflux condenser, a nitrogen inlet tube, a dropper, and a simple trap for removed solvent, followed by thoroughly mixing, and the mixture was heated under a nitrogen stream at 130° C. for 3 hours. Subsequently, 110 parts of ethyl acetate, and 252 parts of diisopropyl malonate were added, and 3 parts of a 28% methanol solution of sodium methoxide was added thereto with stirring under a nitrogen stream, followed by stirring at 65° C. for 8 hours. The amount of isocyanate in the obtained resin solution was 0.12 mol/kg. Furthermore, 683 parts of 4-methyl-2-pentanol was added thereto, and while keeping the temperature of the system at 80 to 85° C., the solvent was distilled off under reduced pressure over 3 hours to obtain 1,010 parts of active methylene-blocked polyisocyanate compound (a5). In the simple trap for the removed solvent, 95 parts of isopropanol was contained. The solid content concentration of the active methylene-blocked polyisocyanate compound (a5) was about 60%.
    • Production of Aqueous Base Coating Composition (B) (Production of Effect Pigment Concentrate)
  • In a stirring mixer, 19 parts of aluminum pigment paste “GX-180A” (trade name, produced by Asahi Kasei Metals Co., Ltd., metal content: 74%), 35 parts of 2-ethyl-1-hexanol, 8 parts of a phosphate group-containing resin solution (note 1), and 0.2 parts of 2-(dimethylamino) ethanol were uniformly mixed to obtain the effect pigment concentrate (P-1).
  • (Note 1) Phosphate group-containing resin solution: A mixed solvent of 27.5 parts of methoxypropanol and 27.5 parts of isobutanol was put in a reaction vessel equipped with a thermometer, a thermostat, a stirrer, a reflux condenser and a dropper and heated at 110° C., and then, 121.5 parts of a mixture containing 25 parts of styrene, 27.5 parts of n-butyl methacrylate, 20 parts of “Isostearyl Acrylate” (trade name, produced by Osaka Organic Chemical Industry, Ltd., branched higher alkyl acrylate), 7.5 parts of 4-hydroxybutyl acrylate, 15 parts of phosphate group-containing polymerizable monomer (note 2), 12.5 parts of 2-methacryloyloxyethyl acid phosphate, 10 parts of isobutanol and 4 parts of tert-butyl peroxyoctanoate was added to the mixed solvent above over 4 hours, and then, a mixture containing 0.5 parts of tert-butyl peroxyoctanoate and 20 parts of isopropanol was further added dropwise over 1 hour, and the resulting mixture was aged with stirring for 1 hour to obtain a phosphate group-containing resin solution having a solid content concentration of 50%. In this resin, the acid value by the phosphate group was 83 mgKOH/g, the hydroxyl value was 29 mgKOH/g, and the weight average molecular weight was 10,000.
  • (Note 2) Phosphate group-containing polymerizable monomer: 57.5 Parts of monobutylphosphoric acid and 41 parts of isobutanol were put in a reaction vessel equipped with a thermometer, a thermostat, a stirrer, a reflux condenser and a dropper, and after raising the temperature to 90° C., 42.5 parts of glycidyl methacrylate was added dropwise over 2 hours. The resulting mixture was further aged with stirring for 1 hour, and thereafter, 59 parts of isopropanol was added to obtain a phosphate group-containing polymerizable monomer solution having a solid content concentration of 50%. In the monomer obtained, the acid value by the phosphate group was 285 mgKOH/g.
  • Production of Aqueous Base Coating Composition (B1) 100 Parts (solid content: 30 parts) of the hydroxyl group-containing acrylic acid aqueous dispersion (i), 73 parts (solid content: 40 parts) of the hydroxyl group-containing water-soluble acrylic resin (ii), 62 parts of the effect pigment concentrate (P-1), and 37.5 parts (solid content: 30 parts) of “CYMEL 325” (trade name, produced by ALLNEX LTD., melamine resin, solid content: 80%) were uniformly mixed, and “PRIMAL ASE-60” (trade name, produced by Rohm & Haas Co., thickener), 2-(dimethylamino)ethanol and deionized water were added thereto to obtain an aqueous base coating composition (B1) having a pH of 8.0, a solid content concentration of coating composition of 25%, and a viscosity of 40 seconds as measured with Ford cup No. 4 at 20° C.
    • Hydroxyl Group-Containing Acrylic Acid Aqueous Dispersion (i):
  • 130 Parts of deionized water and 0.52 parts of “AQUALON KH-10” (trade name, produced by Dai-ichi Kogyo Seiyaku Co., Ltd., polyoxyethylene alkyl ether sulfate ester ammonium salt, active ingredient: 97%) were added to a reaction vessel equipped with a thermometer, a thermostat, a stirrer, a reflux condenser, a nitrogen inlet tube and a dropper, and mixed with stirring in a nitrogen stream, and the temperature was raised to 80° C. Subsequently, a 1% portion of the total amount of the monomer emulsion (1) shown below and 5.3 parts of an aqueous 6% ammonium persulfate solution were introduced into the reaction vessel, followed by keeping it at 80° C. for 15 minutes. The remaining monomer emulsion (1) was then added dropwise over 3 hours to the reaction vessel kept at the same temperature. After the completion of dropwise addition, the mixture was aged for 1 hour.
  • Furthermore, the monomer emulsion (2) shown below was added dropwise over 1 hour and after aging for 1 hour, the mixture was cooled to 30° C. while gradually adding 40 parts of an aqueous 5% 2-(dimethylamino)ethanol solution to the reaction vessel, followed by filtering through a 100-mesh nylon cloth to obtain, as a filtrate, the hydroxyl group-containing acrylic resin aqueous dispersion (i) having an average particle diameter of 120 nm (as measured using a submicron particle size distribution analyzer “COULTER Model N4” (manufactured by Beckman Coulter, Inc.) at 20° C. after dilution with deionized water) and a solid content concentration of 30%. The hydroxyl group-containing acrylic resin aqueous dispersion (i) had an acid value of 33 mgKOH/g and a hydroxyl value of 25 mgKOH/g.
  • Monomer Emulsion (1): 42 Parts of deionized water, 0.72 parts of “AQUALON KH-10”, 2.1 parts of methylenebisacrylamide, 2.8 parts of styrene, 16.1 parts of methyl methacrylate, 28 parts of ethyl acrylate, and 21 parts of n-butyl acrylate were mixed with stirring to obtain the monomer emulsion (1).
  • Monomer Emulsion (2): 18 Parts of deionized water, 0.31 parts of “AQUALON KH-10”, 0.03 parts of ammonium persulfate, 5.1 parts of methacrylic acid, 5.1 parts of 2-hydroxyethyl acrylate, 3 parts of styrene, 6 parts of methyl methacrylate, 1.8 parts of ethyl acrylate, and 9 parts of n-butyl acrylate were mixed with stirring to obtain the monomer emulsion (2).
    • Hydroxyl Group-Containing Water-Soluble Acrylic Resin (ii):
  • 35 Parts of propylene glycol monopropyl ether was added to a flask, and the temperature was raised to 85° C. Subsequently, a mixture of 30 parts of methyl methacrylate, 20 parts of 2-ethylhexyl acrylate, 29 parts of n-butyl acrylate, 15 parts of hydroxyethyl acrylate, 6 parts of acrylic acid, 15 parts of propylene glycol monopropyl ether, and 2.3 parts of 2,2′-azobis(2,4-dimethylvaleronitrile) was added dropwise to the flask over 4 hours, and after the completion of dropwise addition, the mixture was aged for 1 hour. Subsequently, a mixture of 10 parts of propylene glycol monopropyl ether and 1 part of 2,2′-azobis(2,4-dimethylvaleronitrile) was further added dropwise to the flask over 1 hour, and after the completion of dropwise addition, the mixture was aged for 1 hour. Thereafter, 7.4 parts of diethanolamine was further added to obtain the hydroxyl group-containing water-soluble acrylic resin (ii) having a solid content concentration of 55%, an acid value of 47 mgKOH/g, and a hydroxyl value of 72 mgKOH/g.
    • <Production of Clear Coating Composition (C)> (1) Production of Clear Coating Compositions (C1) to (C4)
  • (Production of Hydroxyl Group-Containing Acrylic Resin (c1))
  • Production of Hydroxyl Group-Containing Acrylic Resin (c1-1)
  • 31 Parts of ethoxyethyl propionate was added to a four-necked flask equipped with a stirrer, a thermometer, a condensing tube, and a nitrogen gas inlet opening, and the temperature was raised to 155° C. under a flow of nitrogen gas. After the temperature reached 155° C., the flow of nitrogen gas was stopped, and a mixture of monomers which include 20 Parts of styrene, 35 parts of 2-hydroxypropyl acrylate, 20.8 parts of isobornyl acrylate, 23.5 parts of 2-ethylhexyl acrylate and 0.7 part of acrylic acid (100 parts in total) and 4 parts of di-t-amyl peroxide as a polymerization initiator was added dropwise over 4 hours. Then, the mixture obtained above was aged at 155° C. for 2 hours while flowing nitrogen gas, and after that, the resultant product was cooled to 100° C., followed by diluting with 32.5 parts of butyl acetate to obtain a hydroxyl group-containing acrylic resin (c1-1) solution having a solid content of 60%.
  • The obtained hydroxyl group-containing acrylic resin (c1-1) solution was a homogeneous clear solution having a solid content of 60%. The hydroxyl group-containing acrylic resin (c1-1) had a weight average molecular weight of about 10,000, a hydroxyl value of 151 mgKOH/g and a glass transition temperature of −12° C.
  • (Allophanate Group-Containing Polyisocyanate Compound (c2))
  • The followings were used as the allophanate group-containing polyisocyanate compound.
  • Allophanate group-containing polyisocyanate compound (c2-1): Desmodur (trademark) N3580 produced by Covestro
  • Allophanate group-containing polyisocyanate compound (c2-2): Desmodur (trademark) XP2860 produced by Covestro
    • (Allophanate Group-Free Polyisocyanate Compound)
  • Desmodur (trademark) N3300 and Desmodur (trademark) N3400, both produced by Covestro, were used as the allophanate group-free polyisocyanate compound.
    • (Production of Clear Coating Compositions (C1) to (C4))
  • Each component was uniformly mixed so as to be the blending formulation shown in Table 2. Then, to the obtained mixture, butyl acetate was added to obtain the clear coating compositions (C1) to (C4) having a viscosity of 27 seconds as measured with Ford cup No. 4 at 20° C.
    • <Preparation of Test Plate> (Preparation of Test Material to be Coated)
  • An alloyed hot-dip galvanized steel plate subjected to zinc phosphate treatment was electrodeposition-coated with “ELECRON GT-10” (trade name, produced by Kansai Paint Co., Ltd., ELECRON being a registered trademark, thermosetting epoxy resin-based cationic electrodeposition coating composition) to have a thickness of 20 μm, followed by curing by heating at 170° C. for 30 minutes to prepare a test material to be coated.
    • Example 1
  • (1) The aqueous intermediate coating composition (A1) obtained above was applied to the test material to be coated by a hand spray gun so as to provide a cured film thickness of 15 μm, followed by allowing to stand for 5 minutes, and then, the resultant product was preheated at 80° C. for 3 minutes. Subsequently, the aqueous base coating composition (B1) obtained above was applied to the intermediate coated film by a hand spray gun so as to provide a cured film thickness of 10 μm, followed by allowing to stand for 5 minutes, and then, the resultant product was preheated at 80° C. for 3 minutes.
  • Thereafter, the clear coating composition (C1) obtained above was applied to the uncured base coated film by a hand spray gun so as to provide a cured film thickness of 25 μm, followed by allowing to stand for 7 minutes, and then, the resultant product was heated at 140° C. for 30 minutes, and the whole of the multilayer coated film was thus heat-cured to prepare a test plate.
  • The test plate was further coated with a urethane-based adhesive (trade name: “3740”, produced by Sunstar Inc., wind-shielding agent for automobiles) so as to provide a coated shape having a width of 20 mm, a thickness of 3 mm, and a length of 100 mm or more, and after putting a release paper thereon, they were uniformly pressed with a flat plate. The flat plate was removed, and the test plate was then allowed to stand at a temperature of 23±2° C. and a humidity of 50±5% for 72 hours to cure the adhesive. After that, the release paper was peeled to prepare the test plate A for WDB (glass adhesion) test.
  • (2) The aqueous intermediate coating composition (A1) obtained above was applied to the test material to be coated by a hand spray gun so as to provide a cured film thickness of 20 μm, followed by allowing to stand for 5 minutes, and the resultant product was preheated at 80° C. for 3 minutes. Subsequently, the aqueous base coating composition (B1) obtained above was applied to the intermediate coated film by a hand spray gun so as to provide a cured film thickness of 15 μm, followed by allowing to stand for 5 minutes, and then, the resultant product was preheated at 80° C. for 3 minutes.
  • Thereafter, the clear coating composition (C1) obtained above was applied to the uncured base coated film by a hand spray gun so as to provide a cured film thickness of 35 μm, followed by allowing to stand for 7 minutes, and the resultant product was heated at 140° C. for 30 minutes, and the whole of the multilayer coated film was thus heat-cured to prepare the test plate B for chipping resistance test, scratch resistance test and coated film hardness test.
    • Examples 2 to 11 and Comparative Examples 1 to 8
  • Each test plate (two kinds) was prepared in the same manner as in Example 1 except that the aqueous intermediate coating composition (A) was changed to the aqueous intermediate coating compositions (A2) to (A16), respectively, and the clear coating composition (C) was changed to the clear coating compositions (C2) to (C4), respectively.
  • With respect to each of the test plates obtained, the WDB adhesion (glass adhesion) test, chipping resistance test, scratch resistance test and coated film hardness test were performed based on the following test methods and evaluation methods. In addition, the elongation at break, Young's modulus and Tukon hardness of the intermediate coated film were also measured by the above-described measurement methods. The test results are shown together in Table 2.
    • <WDB Adhesion (Glass Adhesion)>
  • Each test plate A prepared above was immersed in a constant-temperature water bath set at 40° C. for 240 hours and then cooled by immersing it in water at 23° C. for 1 hour, and then, the following peel test was performed.
  • A cut reaching the coated film surface was formed at an angle of about 60° relative to the coated film by a cutter knife at intervals of 2 to 3 mm while manually pulling the cured adhesive layer in the direction at 90° or more relative to the coated film.
  • The peeled state after peeling the adhesive layer was evaluated in accordance with the following criteria “AA”, “A”, “B”, and “C”. In the following criteria, AA and A are regarded as being accepted.
  • AA: Separation of the adhesive layer was not observed, and exposure of the coated film was not observed.
  • A: The coated film was not broken and only the adhesive layer was separated by cohesion failure, but adhesion between the coated film and the adhesive layer was substantially maintained.
  • B: The coated film was separated by cohesion failure.
  • C: Separation was observed at the interface between the coated film and the adhesive layer.
    • <Chipping Resistance>
  • The test plate B was placed on a sample holder of a flying stone chipping tester Model JA-400 (chipping test device) manufactured by Suga Test Instruments Co., Ltd., and 50 g of crushed granite stone with a particle size of No. 7 was hit against the test plate B at an angle of 45° by blowing compressed air at 0.392 MPa (4 kgf/cm2) from a distance of 30 cm at −20° C. Thereafter, the resulting test plate B was washed with water and dried, and a cloth pressure-sensitive adhesive tape (produced by Nichiban Co., Ltd.) was stuck to the coating surface. After peeling off the tape, scratch occurrence on the coated film were observed with an eye and the evaluation was made in accordance with the following criteria. In the following criteria, AA and A are regarded as being accepted.
  • AA: The scratch size was extremely small, and the electrodeposition surface or raw steel plate was not exposed.
  • A: The scratch size was small, and the electrodeposition surface or raw steel plate was not exposed.
  • B: The scratch size was small, but the electrodeposition surface or raw steel plate was exposed.
  • C: The scratch size was considerably large, and the raw steel plate was also largely exposed.
    • <Scratch Resistance>
  • The test plate B was stuck to an automobile with a water resistant tape produced by Nichiban Co., Ltd., and the automobile was washed with an automobile washing machine for 15 times under the condition of 20° C. After that, 20° mirror specular reflectance (20° gloss value) of the test plate B was measured and the gloss retention rate (%) with respect to the 20° gloss value before the test was measured, and the evaluation was made in accordance with the following criteria. The higher the gloss retention rate is, the better the scratch resistance is. As the automobile washing machine, “PO 20 FWRC” produced by Yasui Sangyo Co., Ltd. was used. In the following criteria, AA and A are regarded as being accepted.
  • AA: The gloss retention rate is 85% or more
  • A+: The gloss retention rate is 80% or more and less than 85%
  • A: The gloss retention rate is 70% or more and less than 80%
  • B: The gloss retention rate is 60% or more and less than 70%
  • C: The gloss retention rate is less than 60%
    • <Coated Film Hardness>
  • The coated film hardness was measured using a TUKON hardness tester (TUKON microhardness tester, produced by American Chain & Cable Company) after leaving the test plate B in a constant-temperature chamber at 20° C. for 4 hours. The higher the value is, the harder the coated film is. In the following criteria, AA and A are regarded as being accepted.
  • AA: The hardness is 10 or more
  • A: The hardness is 5 or more and less than 10
  • B: The hardness is less than 5
  • TABLE 2
    Tg Example
    (° C.) Mw 1 2 3 4 5 6 7
    Aqueous Pigment Hydroxyl group- 5 35,000 20 20 20 20 20
    intermediate dispersion containing acrylic resin
    coating paste (a1-1)
    composition Hydroxyl group- 14 34,000 20 20
    containing acrylic resin
    (a1-2)
    Hydroxyl group- 21 33,000
    containing acrylic resin
    (a1-3)
    Hydroxyl group- 0 34,000
    containing acrylic resin
    (a1-4)
    Hydroxyl group- 10 25,000
    containing acrylic resin
    (a1-5)
    Hydroxyl group- 15 45,000
    containing acrylic resin
    (a1-6)
    Hydroxyl group-containing polyester resin
    (a3)
    “JR-806” 90 90 90 90 90 90 90
    “Carbon MA-100” 0.1 0.1 0.1 0.1 0.1 0.1 0.1
    Tg Example
    (° C.) Mw 8 9 10 11 12 13
    Aqueous Pigment Hydroxyl group- 5 35,000 20 20 20 20
    intermediate dispersion containing acrylic resin
    coating paste (a1-1)
    composition Hydroxyl group- 14 34,000 20 20
    containing acrylic resin
    (a1-2)
    Hydroxyl group- 21 33,000
    containing acrylic resin
    (a1-3)
    Hydroxyl group- 0 34,000
    containing acrylic resin
    (a1-4)
    Hydroxyl group- 10 25,000
    containing acrylic resin
    (a1-5)
    Hydroxyl group- 15 45,000
    containing acrylic resin
    (a1-6)
    Hydroxyl group-containing polyester resin
    (a3)
    “JR-806” 90 90 90 90 90 90
    “Carbon MA-100” 0.1 0.1 0.1 0.1 0.1 0.1
    Tg Example
    (° C.) Mw 1 2 3 4 5 6 7
    Aqueous Hydroxyl group-containing 5 35,000  5 10 10
    intermediate acrylic resin (a1-1)
    coating Hydroxyl group-containing 14 34,000 10
    composition acrylic resin (a1-2)
    Hydroxyl group-containing 21 33,000
    acrylic resin (a1-3)
    Hydroxyl group-containing 0 34,000
    acrylic resin (a1-4)
    Hydroxyl group-containing 10 25,000
    acrylic resin (a1-5)
    Hydroxyl group-containing 15 45,000
    acrylic resin (a1-6)
    Polyurethane resin (a2-1) −65 polyether 10 10 10 10 10 10 10
    skeleton
    Polyurethane resin (a2-2) −38 polyester
    skeleton
    Acryl/polyurethane ratio 20/10 25/10 30/10 20/10 30/10 20/10 30/10
    Hydroxyl group-containing polyester resin (a3) 30 25 20 30 20 30 20
    Melamine resin (a4) 30 30 30 25 25 30 30
    Active methylene-blocked polyisocyanate compound 10 10 10 15 15 10 10
    (a5)
    Aqueous intermediate coating composition A1 A2 A3 A4 A5 A6 A7
    Tg Example
    (° C.) Mw 8 9 10 11 12 13
    Aqueous Hydroxyl group-containing 5 35,000  5  5  5  5
    intermediate acrylic resin (a1-1)
    coating Hydroxyl group-containing 14 34,000 10
    composition acrylic resin (a1-2)
    Hydroxyl group-containing 21 33,000
    acrylic resin (a1-3)
    Hydroxyl group-containing 0 34,000
    acrylic resin (a1-4)
    Hydroxyl group-containing 10 25,000
    acrylic resin (a1-5)
    Hydroxyl group-containing 15 45,000
    acrylic resin (a1-6)
    Polyurethane resin (a2-1) −65 polyether 10 10 10 10 10 10
    skeleton
    Polyurethane resin (a2-2) −38 polyester
    skeleton
    Acryl/polyurethane ratio 20/10 30/10 25/10 25/10 25/10 25/10
    Hydroxyl group-containing polyester resin (a3) 30 20 25 25 25 25
    Melamine resin (a4) 25 25 30 30 30 30
    Active methylene-blocked polyisocyanate compound 15 15 10 10 10 10
    (a5)
    Aqueous intermediate coating composition A8 A9 A2 A2 A2 A2
    Example
    1 2 3 4 5 6 7
    Aqueous base coating composition B1 B1 B1 B1 B1 B1 B1
    Clear Hydroxyl group-containing acrylic resin (c1) c1-1 64.4 64.4 64.4 64.4 64.4 64.4 64.4
    coating allophanate group-containing c2-1 36 36 36 36 36 36 36
    composition polyisocyanate compound (c2) c2-2
    allophanate group-free polyisocyanate N3300
    compound
    allophanate group-free polyisocyanate N3400
    compound
    Clear coating composition C1 C1 C1 C1 C1 C1 C1
    Physical Elongation [%] 26 23 21 29 26 22 20
    properties of Young's modulus [kgf/cm2] 5,200 5,500 6,000 5,000 5,200 5,800 5,900
    intermediate Tukon Hardness 5.0 5.5 5.8 4.8 5.1 5.7 5.7
    coated film
    Evaluation WDB Adhesion A AA AA A A AA AA
    results Chipping resistance AA AA A AA AA A A
    Scratch resistance AA AA AA AA AA AA AA
    Coated film hardness AA AA AA AA AA AA AA
    Example
    8 9 10 11 12 13
    Aqueous base coating composition B1 B1 B1 B1 B1 B1
    Clear Hydroxyl group-containing acrylic resin (c1) c1-1 64.4 64.4 64.4 64.4 64.4 64.4
    coating allophanate group-containing c2-1 36 36 26 26 12
    composition polyisocyanate compound (c2) c2-2 36
    allophanate group-free polyisocyanate N3300 10 12
    compound
    allophanate group-free polyisocyanate N3400 10 12
    compound
    Clear coating composition C1 C1 C2 C3 C4 C5
    Physical Elongation [%] 25 23 23 23 23 23
    properties of Young's modulus [kgf/cm2] 5,500 5,600 5,500 5,500 5,500 5,500
    intermediate Tukon Hardness 5.4 5.5 5.5 5.5 5.5 5.5
    coated film
    Evaluation WDB Adhesion A AA AA AA AA AA
    results Chipping resistance AA AA AA AA AA AA
    Scratch resistance AA AA A+ A A A
    Coated film hardness AA AA AA A A A
    Tg Comparative Example
    (° C.) Mw 1 2 3 4
    Aqueous Pigment Hydroxyl group-containing acrylic resin (a1-1) 5 35,000 20 20
    intermediate dispersion Hydroxyl group-containing acrylic resin (a1-2) 14 34,000
    coating paste Hydroxyl group-containing acrylic resin (a1-3) 21 33,000 20
    composition Hydroxyl group-containing acrylic resin (a1-4) 0 34,000 20
    Hydroxyl group-containing acrylic resin (a1-5) 10 25,000
    Hydroxyl group-containing acrylic resin (a1-6) 15 45,000
    Hydroxyl group-containing polyester resin (a3)
    “JR-806” 90 90 90 90
    “Carbon MA-100”   0.1   0.1   0.1   0.1
    Hydroxyl group-containing acrylic resin (a1-1) 5 35,000 20
    Hydroxyl group-containing acrylic resin (a1-2) 14 34,000
    Hydroxyl group-containing acrylic resin (a1-3) 21 33,000
    Hydroxyl group-containing acrylic resin (a1-4) 0 34,000
    Hydroxyl group-containing acrylic resin (a1-5) 10 25,000
    Hydroxyl group-containing acrylic resin (a1-6) 15 45,000
    Polyurethane resin (a2-l) −65 polyether 10 10 10
    skeleton
    Polyurethane resin (a2-2) −38 polyester 10
    skeleton
    Acryl/polyurethane ratio 40/10 20/10 20/10 20/10
    Hydroxyl group-containing polyester resin (a3) 10 30 30 30
    Melamine resin (a4) 30 30 30 30
    Active methylene-blocked polyisocyanate compound (a5) 10 10 10 10
    Aqueous intermediate coating composition A10 A11 A12 A13
    Tg Comparative Example
    (° C.) Mw 5 6 7 8
    Aqueous Pigment Hydroxyl group-containing acrylic resin (a1-1) 5 35,000 20
    intermediate dispersion Hydroxyl group-containing acrylic resin (a1-2) 14 34,000 10
    coating paste Hydroxyl group-containing acrylic resin (a1-3) 21 33,000
    composition Hydroxyl group-containing acrylic resin (a1-4) 0 34,000
    Hydroxyl group-containing acrylic resin (a1-5) 10 25,000 20
    Hydroxyl group-containing acrylic resin (a1-6) 15 45,000 20
    Hydroxyl group-containing polyester resin (a3) 10
    “JR-806” 90 90 90 90
    “Carbon MA-100”   0.1   0.1   0.1   0.1
    Hydroxyl group-containing acrylic resin (a1-1) 5 35,000  5
    Hydroxyl group-containing acrylic resin (a1-2) 14 34,000
    Hydroxyl group-containing acrylic resin (a1-3) 21 33,000
    Hydroxyl group-containing acrylic resin (a1-4) 0 34,000
    Hydroxyl group-containing acrylic resin (a1-5) 10 25,000
    Hydroxyl group-containing acrylic resin (a1-6) 15 45,000 10
    Polyurethane resin (a2-l) −65 polyether 10 10 10 10
    skeleton
    Polyurethane resin (a2-2) −38 polyester
    skeleton
    Acryl/polyurethane ratio 20/10 30/10 10/10 25/10
    Hydroxyl group-containing polyester resin (a3) 30 20 30 25
    Melamine resin (a4) 30 30 30 30
    Active methylene-blocked polyisocyanate compound (a5) 10 10 10 10
    Aqueous intermediate coating composition A14 A15 A16 A2
    Comparative Example
    1 2 3 4
    Aqueous base coating composition B1 B1 B1 B1
    Clear coating Hydroxyl group-containing acrylic resin (c1) c1-1 64.4 64.4 64.4 64.4
    composition allophanate group-containing polyisocyanate c2-1 36 36 36 36
    compound (c2) c2-2
    allophanate group-free polyisocyanate N3300
    compound
    allophanate group-free polyisocyanate N3400
    compound
    Clear coating composition C1 C1 C1 C1
    Physical properties of Elongation [%] 11 9 15 35
    intermediate coated Young's modulus [kgf/cm2] 7,000 8,000 6,500 4,000
    film Tukon Hardness 6.5 7.5 6.0 3.4
    Evaluation results WDB Adhesion AA AA AA C
    Chipping resistance C C B A
    Scratch resistance AA AA AA AA
    Coated film hardness AA AA AA AA
    Comparative Example
    5 6 7 8
    Aqueous base coating composition B1 B1 B1 B1
    Clear coating Hydroxyl group-containing acrylic resin (c1) c1-1 64.4 64.4 64.4 64.4
    composition allophanate group-containing polyisocyanate c2-1 36 36 36
    compound (c2) c2-2
    allophanate group-free polyisocyanate N3300 36
    compound
    allophanate group-free polyisocyanate N3400
    compound
    Clear coating composition C1 C1 C1 C6
    Physical properties of Elongation [%] 34 17 35 23
    intermediate coated Young's modulus [kgf/cm2] 4,500 6,500 4,200 5,500
    film Tukon Hardness 3.8 6.2 3.3 5.5
    Evaluation results WDB Adhesion B AA B AA
    Chipping resistance B B B AA
    Scratch resistance AA AA AA B
    Coated film hardness AA AA AA B
  • As seen from the results in Table 2, in all of Examples 1 to 13, a multilayer coated film having good performance in terms of both the chipping resistance and the adhesion to a glass member and also having excellent scratch resistance and coated film hardness could be formed. On the other hand, in Comparative Examples 1 to 7 in which the aqueous intermediate coating composition does not satisfy the requirement(s) specified in the present invention, it was impossible to satisfy both the chipping resistance and the adhesion to a glass member. In Comparative Example 8 in which the clear coating composition does not satisfy the requirement(s) specified in the present invention, the chipping resistance and the adhesiveness to the glass member were good, but the scratch resistance and the coated film hardness were not enough to compatible with each other.
  • While the present invention is described in detail and with reference to specific embodiments thereof, it is apparent to one skilled in the art that various changes and modifications may be made therein without departing from the spirit and scope thereof.

Claims (1)

What is claimed is:
1. A method for forming a multilayer coated film on an electrodeposition-coated alloyed hot-dip galvanized steel plate, the method comprising the following steps (1) to (4):
step (1): applying an aqueous intermediate coating composition (A) to an electrodeposition coated film, thereby forming an intermediate coated film on the electrodeposition coated film;
step (2): after preheating, applying an aqueous base coating composition (B) to the intermediate coated film, thereby forming a base coated film on the intermediate coated film;
step (3): after preheating, applying a clear coating composition (C) to the base coated film, thereby forming a clear coated film on the base coated film; and
step (4): heat-curing the intermediate coated film formed in the step (1), the base coated film formed in the step (2) and the clear coated film formed in the step (3),
wherein the aqueous intermediate coating composition (A) contains a hydroxyl group-containing acrylic resin (a1) having a glass transition temperature (Tg) of 5 to 15° C. and a weight average molecular weight of 30,000 to 40,000, a polyurethane resin (a2) having a glass transition temperature (Tg) of −50° C. or less and having a polyether skeleton, a hydroxyl group-containing polyester resin (a3), a melamine resin (a4), and an active methylene-blocked polyisocyanate compound (a5), a ratio of the hydroxyl group-containing acrylic resin (a1) to the polyurethane resin (a2) is from 20/10 to 30/10 in terms of solid content ratio, and the heat-cured coated film of the aqueous intermediate coating composition (A) has an elongation at break at 20° C. of 20 to 30%, a Young's modulus of 5,000 to 6,000 kgf/cm2, and a Tukon hardness of 4 to 6, and
wherein the clear coating composition (C) contains a hydroxyl group-containing acrylic resin (c1) and an allophanate group-containing polyisocyanate compound (c2).
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Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111014397A (en) * 2019-12-26 2020-04-17 泰州汇锦电子有限公司 Stamping part for television and manufacturing method thereof
JP6967624B2 (en) * 2020-03-13 2021-11-17 大日本塗料株式会社 Printed matter and its manufacturing method
CN115073949B (en) * 2021-03-02 2024-07-12 荒川化学工业株式会社 Aqueous composition, cured product, and laminate
US20240309239A1 (en) 2021-04-28 2024-09-19 Kansai Paint Co., Ltd. Aqueous coating material composition and method for forming multilayer coating film
JP7534265B2 (en) 2021-06-15 2024-08-14 日本ペイント・オートモーティブコーティングス株式会社 Water-based paint composition and method for forming multi-layer coating film
JPWO2023157917A1 (en) 2022-02-18 2023-08-24
JP2024090534A (en) * 2022-12-23 2024-07-04 日産自動車株式会社 Multi-layer coating film formation method

Family Cites Families (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6123650A (en) * 1984-07-11 1986-02-01 Nissan Motor Co Ltd Chipping-resistant coating
CA2179561A1 (en) * 1995-06-27 1996-12-28 Hideki Takayama Coating composition and method for forming multi-layer coating
EP1038935A4 (en) * 1997-10-20 2001-08-29 Kansai Paint Co Ltd Coating composition and method for coating therewith
US20030102217A1 (en) * 2001-08-31 2003-06-05 Kansai Paint Co., Ltd Method for forming multilayer coating film
JP3831266B2 (en) * 2002-01-22 2006-10-11 日本ペイント株式会社 Coating method
JP2004075781A (en) * 2002-08-13 2004-03-11 Nippon Polyurethane Ind Co Ltd Method for producing allophanate-modified block polyisocyanate
GB2397578B (en) * 2002-12-17 2004-12-08 Ici Plc Aqueous dispersions of polyurethane-addition polymer hybrid particles especially for use in coating compositions
US7871669B2 (en) * 2004-08-30 2011-01-18 E.I. Du Pont De Nemours And Company Method for achieving a durable two-tone finish on a vehicle
CA2535993C (en) * 2005-02-22 2008-11-18 Kansai Paint Co., Ltd. Aqueous intermediate coating composition and method for forming multilayer coating film
JP2006239535A (en) 2005-03-02 2006-09-14 Nippon Paint Co Ltd Multilayer coating film for body of car
WO2007119305A1 (en) 2006-03-15 2007-10-25 Kansai Paint Co., Ltd. Coating composition and method of forming coating film
WO2008050778A1 (en) * 2006-10-18 2008-05-02 Kansai Paint Co., Ltd. Method for coating plastic molded article
US8563636B2 (en) * 2006-10-23 2013-10-22 Kansai Paint Co., Ltd. Aqueous two-package type clear coating composition and process for the formation of multilayer finish coating film
GB2447741B (en) * 2007-03-12 2009-06-17 Kansai Paint Co Ltd Method for making multilayer coating film
JP5037419B2 (en) 2008-04-22 2012-09-26 日本ペイント株式会社 Formation method of multilayer coating film
JP4701293B2 (en) * 2009-01-23 2011-06-15 関西ペイント株式会社 Multi-layer coating formation method
CN102395637A (en) 2009-04-16 2012-03-28 株式会社德山 Primer composition for optical articles, and optical article
JP5143078B2 (en) 2009-04-24 2013-02-13 マツダ株式会社 Multi-layer coating formation method
JPWO2011040374A1 (en) * 2009-09-29 2013-02-28 関西ペイント株式会社 Multi-layer coating formation method
CN102959019B (en) * 2010-07-02 2015-05-13 关西涂料株式会社 Method for forming multilayer coating film
EP2719733B1 (en) 2011-07-12 2016-03-16 Honda Motor Co., Ltd. Clear coating composition and method for coating automobile body
CN104136135A (en) 2012-03-01 2014-11-05 本田技研工业株式会社 Method for forming multilayered coating film
CN104321395B (en) 2012-04-03 2018-03-20 关西涂料株式会社 Water-based paint compositions and the method for forming film
JP6392801B2 (en) 2016-03-02 2018-09-19 関西ペイント株式会社 Multi-layer coating formation method
JP6466977B2 (en) 2017-02-15 2019-02-06 トヨタ自動車株式会社 Multi-layer coating formation method

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